Volume42: OrganophosphorusCompounds (incl.RO—PandRN—P) · 2020. 11. 3. · 42.4.1.7.2 Variation 2: Reduction of Alkylphosphonates with Lithium Aluminum Hydride .....94 42.4.1.7.3

Volume 42:Organophosphorus Compounds(incl. RO—P and RN—P)

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V

Volume Editor�s Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII

Table of Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XI

IntroductionF. Mathey . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

42.1 Product Class 1: Phosphinidenes and Terminal Phosphinidene ComplexesJ. C. Slootweg and K. Lammertsma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

42.2 Product Class 2: Oxo-, Thioxo-, Selenoxo-, and Iminophosphinesand DiphosphenesM. Yoshifuji . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

42.3 Product Class 3: Phosphenium SaltsM. Yoshifuji . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

42.4 Product Class 4: AlkylphosphinesE. Hey-Hawkins and A. A. Karasik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

42.5 Product Class 5: Bis(alkylphosphino)- and Poly(alkylphosphino)alkanes,and Di- and Polyphosphines with a P—P BondE. Hey-Hawkins and A. A. Karasik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

42.6 Product Class 6: Cyclic PhosphinesD. Gudat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155

42.7 Product Class 7: Dialkylphosphinous Acids and DerivativesK. M. Pietrusiewicz and M. Stankevič . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221

42.8 Product Class 8: Alkylphosphonous Acids and DerivativesK. M. Pietrusiewicz and M. Stankevič . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243

42.9 Product Class 9: Phosphorous Acid and DerivativesM. Stankevič and K. M. Pietrusiewicz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275

42.10 Applications of Tricoordinated Phosphorus Compoundsin Homogeneous Catalysis

42.10.1 General Catalytic MethodsM. Toffano . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347

42.10.2 Enantioselective Catalytic MethodsJ.-C. Fiaud and A. Marinetti . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391

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Science of Synthesis Original Edition Volume 42 © Georg Thieme Verlag KG

42.11 Applications of Tricoordinated Phosphorus Compounds inOrganocatalysisJ. L. Methot and W. R. Roush . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469

42.12 Product Class 12: Alkylphosphonium SaltsD. Virieux, J.-N. Volle, and J.-L. Pirat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503

42.13 Product Class 13: Trialkylphosphine Oxides, Sulfides, Selenides,Tellurides, and ImidesN. L. Kilah and S. B. Wild . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595

42.14 Product Class 14: Dialkylphosphinic Acids and DerivativesJ. Drabowicz, J. Lewkowski, C. V. Stevens, D. Krasowska, and R. Karpowicz . . 633

42.15 Product Class 15: Alkylphosphonic Acids and DerivativesJ. Drabowicz, P. Kiełbasiński, P. Łyżwa, M. Mikołajczyk, and A. Zaja̧c . . . . . . . . . 679

42.16 Product Class 16: Phosphoric Acid and DerivativesC. E. McKenna, B. A. Kashemirov, and K. M. Błażewska . . . . . . . . . . . . . . . . . . . . . 779

42.17 Product Class 17: PhosphazenesS. Urgaonkar and J. G. Verkade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923

42.18 Product Class 18: Pentacoordinated PhosphoranesT. Kawashima and J. Kobayashi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 953

42.19 Product Class 19: Hexacoordinated PhosphatesD. Linder and J. Lacour . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 977

Keyword Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 993

Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1049

Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1121

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IntroductionF. Mathey

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

42.1 Product Class 1: Phosphinidenes and Terminal Phosphinidene ComplexesJ. C. Slootweg and K. Lammertsma

42.1 Product Class 1: Phosphinidenes and Terminal Phosphinidene Complexes . 15

42.1.1 Product Subclass 1: Free Phosphinidenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

42.1.1.1 Synthesis of Product Subclass 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

42.1.1.1.1 Method 1: Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1642.1.1.1.1.1 Variation 1: Thermal Generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1642.1.1.1.1.2 Variation 2: Photolytic Generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1642.1.1.1.2 Method 2: Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1742.1.1.1.3 Method 3: Phospha-Wittig Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

42.1.1.2 Applications of Product Subclass 1 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . 18

42.1.1.2.1 Method 1: Trapping Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

42.1.2 Product Subclass 2: Neutral Electrophilic Phosphinidene Complexes . . . . . . 19


42.1.2.1.1 Method 1: Cheletropic Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2042.1.2.1.1.1 Variation 1: From 7-Phosphanorbornadienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2042.1.2.1.1.2 Variation 2: From Phosphiranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2242.1.2.1.1.3 Variation 3: From Phosphirenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2242.1.2.1.2 Method 2: Salt Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23


42.1.2.2.1 Method 1: Trapping Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

42.1.3 Product Subclass 3: Cationic Electrophilic Phosphinidene Complexes . . . . . 24


42.1.3.1.1 Method 1: Chloride Abstraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

42.1.4 Product Subclass 4: Nucleophilic Phosphinidene Complexes . . . . . . . . . . . . . . 25


42.1.4.1.1 Method 1: Salt Metathesis/Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2542.1.4.1.1.1 Variation 1: Of Metal Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2642.1.4.1.1.2 Variation 2: Of Alkali Metal Phosphides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2642.1.4.1.1.3 Variation 3: Of Transition Metal Phosphides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2842.1.4.1.2 Method 2: Addition/Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2942.1.4.1.3 Method 3: Dehydrohalogenation/Ligation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3042.1.4.1.4 Method 4: a-Hydrogen Migration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3142.1.4.1.5 Method 5: Oxidation/Deprotonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

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42.1.4.2.1 Method 1: Phosphinidene-Transfer Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

42.2 Product Class 2: Oxo-, Thioxo-, Selenoxo-, and Iminophosphines andDiphosphenesM. Yoshifuji

42.2 Product Class 2: Oxo-, Thioxo-, Selenoxo-, and Iminophosphines andDiphosphenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

42.2.1 Product Subclass 1: Oxophosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37


42.2.1.1.1 Method 1: Elimination Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3742.2.1.1.2 Method 2: Cycloreversion Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

42.2.2 Product Subclass 2: Thioxophosphines and Selenoxophosphines . . . . . . . . . . 39


42.2.2.1.1 Method 1: Elimination Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4042.2.2.1.2 Method 2: Cycloreversion Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4042.2.2.1.3 Methods 3: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

42.2.3 Product Subclass 3: Iminophosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44


42.2.3.1.1 Method 1: Elimination Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4442.2.3.1.2 Method 2: Substitution Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4542.2.3.1.3 Method 3: Cycloreversion Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

42.2.4 Product Subclass 4: Diphosphenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47


42.2.4.1.1 Method 1: Elimination and/or Condensation Reactions . . . . . . . . . . . . . . . . . . 4742.2.4.1.2 Method 2: Rearrangement Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5142.2.4.1.3 Method 3: Substitution Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

42.2.5 Product Subclass 5: Heteroatom-Substituted Diphosphenes . . . . . . . . . . . . . . 53

42.2.6 Product Subclass 6: Stereodefined Diphosphenes . . . . . . . . . . . . . . . . . . . . . . . . . 54

42.2.7 Product Subclass 7: Heteroatom-Substituted Iminophosphines . . . . . . . . . . . 56


42.2.7.1.1 Method 1: Elimination Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5642.2.7.1.2 Method 2: Substitution Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

42.2.8 Product Subclass 8: Tetraphosphenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58


42.2.8.1.1 Method 1: Activation of White Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

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42.3 Product Class 3: Phosphenium SaltsM. Yoshifuji

42.3 Product Class 3: Phosphenium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

42.3.1 Synthesis of Product Class 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63

42.3.1.1 Method 1: Halogen Abstraction of Halophosphines . . . . . . . . . . . . . . . . . . . . . 6342.3.1.2 Method 2: Alkylation or Protonation of Diphosphenes . . . . . . . . . . . . . . . . . . . 66

42.3.2 Applications of Product Class 3 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . 67

42.3.2.1 Method 1: Reactions of Phosphenium Cations with UnsaturatedHydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

42.4 Product Class 4: AlkylphosphinesE. Hey-Hawkins and A. A. Karasik

42.4 Product Class 4: Alkylphosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

42.4.1 Synthesis of Product Class 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

42.4.1.1 Method 1: Synthesis from Phosphine, or Primary or SecondaryPhosphines, and Alkyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

42.4.1.1.1 Variation 1: From Phosphine and Alkyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . 7342.4.1.1.2 Variation 2: From Primary Phosphines and Alkyl Halides . . . . . . . . . . . . . . . . . . 7442.4.1.1.3 Variation 3: From Secondary Phosphines and Alkyl or Acyl Halides . . . . . . . . 7542.4.1.2 Method 2: Synthesis from Metal Organophosphides and Electrophiles . . . 7542.4.1.2.1 Variation 1: Synthesis from Metal Organophosphides and Alkyl Halides . . . 7542.4.1.2.2 Variation 2: Synthesis from Metal Organophosphides and Esters . . . . . . . . . . 7942.4.1.2.3 Variation 3: Ring Opening of Tetrahydrofuran . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8042.4.1.3 Method 3: Addition of Phosphines to C—X Multiple Bonds . . . . . . . . . . . . . . . 8142.4.1.3.1 Variation 1: Addition to Alk-1-enes or Cyclic Alkenes . . . . . . . . . . . . . . . . . . . . . 8142.4.1.3.2 Variation 2: Addition to Carbonyl Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8342.4.1.3.3 Variation 3: Mannich-Type Reactions of Phosphines, Formaldehyde,

and Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8342.4.1.4 Method 4: Synthesis from Halophosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8342.4.1.4.1 Variation 1: From Phosphorus Trihalides or Trialkyl Phosphites and

Organometallic Alkali Metal Compounds or Grignard Reagents 8342.4.1.4.2 Variation 2: From Alkyldihalophosphines and Organometallic Alkali Metal

Compounds or Grignard Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . 8642.4.1.4.3 Variation 3: From Dialkylhalophosphines and Organometallic Alkali Metal

Compounds or Grignard Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . 8742.4.1.4.4 Variation 4: From Chlorophosphines and Other Organometallic Reagents . 9042.4.1.5 Method 5: Cleavage of Diphosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9042.4.1.6 Method 6: Synthesis from Elemental Phosphorus and Alkyl Halides,

Alcohols, or Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9142.4.1.7 Method 7: Reduction of Halophosphines, Phosphinic Acids, Phosphinic

Acid Esters or Halides, and Trialkyl- and DialkylphosphineOxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

42.4.1.7.1 Variation 1: Reduction of Halophosphines with Lithium AluminumHydride or Other Metal Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

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42.4.1.7.2 Variation 2: Reduction of Alkylphosphonates with Lithium AluminumHydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94

42.4.1.7.3 Variation 3: Reduction of Dialkylphosphine Oxides, Dialkylphosphinates,or Alkylphosphonates with Aluminum Derivatives . . . . . . . . . . . 94

42.4.1.7.4 Variation 4: Reduction of Trialkylphosphine Oxides with LithiumAluminum Hydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

42.4.1.7.5 Variation 5: Reduction of Dialkylphosphine Oxides, Dialkylphosphinates,or Alkylphosphinates with Silanes . . . . . . . . . . . . . . . . . . . . . . . . . . 97

42.4.1.8 Method 8: Reduction of Trialkylphosphine Sulfides and P-ChiralPhosphine–Borane Complexes Bearing an Alkylsulfanyl Group 98

42.4.1.8.1 Variation 1: With Alkali Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9842.4.1.8.2 Variation 2: With Lithium Aluminum Hydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9942.4.1.9 Method 9: Synthesis from Quaternary Phosphonium Salts . . . . . . . . . . . . . . 10042.4.1.9.1 Variation 1: Synthesis from Tetrakis(hydroxymethyl)phosphonium

Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10042.4.1.10 Method 10: Disproportionation of Dialkylphosphine Oxides . . . . . . . . . . . . . 10142.4.1.11 Method 11: Addition Reactions of Unsaturated Tertiary Vinylphosphines . 10142.4.1.12 Method 12: Enantioselective Cleavage of a P—C Bond in Alkyldimethyl-

phosphine–Borane Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102

42.5 Product Class 5: Bis(alkylphosphino)- and Poly(alkylphosphino)alkanes,and Di- and Polyphosphines with a P—P BondE. Hey-Hawkins and A. A. Karasik

42.5 Product Class 5: Bis(alkylphosphino)- and Poly(alkylphosphino)alkanes,and Di- and Polyphosphines with a P—P Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

42.5.1 Product Subclass 1: Bis(alkylphosphino)- andPoly(alkylphosphino)alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109


42.5.1.1.1 Method 1: Synthesis from Metal Dialkylphosphides and AliphaticElectrophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110

42.5.1.1.1.1 Variation 1: Synthesis from Dialkylphosphides or Dialkylphosphinesand Polyhaloalkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110

42.5.1.1.1.2 Variation 2: Synthesis from Dialkylphosphides and Cyclic Sulfates . . . . . . . . 11542.5.1.1.1.3 Variation 3: Synthesis from Dialkylphosphides and (Dialkylphosphino)alkyl

Sulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11642.5.1.1.1.4 Variation 4: Synthesis from Dialkylphosphines and Polyhaloalkanes,

Alkylamines, and Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11842.5.1.1.1.5 Variation 5: Synthesis from Alkylphosphides and Dihaloalkanes . . . . . . . . . . 11942.5.1.1.1.6 Variation 6: Synthesis from Bis(alkylphosphides) and Alkyl Halides . . . . . . . 12042.5.1.1.2 Method 2: Synthesis from Metal Phosphinomethanides and

Electrophiles Containing Phosphino Groups . . . . . . . . . . . . . . . . . 12042.5.1.1.2.1 Variation 1: Synthesis from (Dialkylphosphino)methanides and

Dialkylhalophosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12042.5.1.1.2.2 Variation 2: Enantioselective Synthesis from Lithium (Dialkylphosphi-

no)methanide–Borane Complexes and Alkylhalophosphines . 122

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42.5.1.1.2.3 Variation 3: Synthesis from Poly(dialkylphosphino)methanides andDialkylhalophosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123

42.5.1.1.2.4 Variation 4: Synthesis from [(Dialkylphosphino)methyl]silanes or-stannanes and Dialkylhalophosphines . . . . . . . . . . . . . . . . . . . . . . 124

42.5.1.1.2.5 Variation 5: Oxidative Coupling of (Dialkylphosphino)methanides . . . . . . . . 12542.5.1.1.2.6 Variation 6: Synthesis from (Dialkylphosphino)methanides and

Polyhaloalkanes or Analogues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12742.5.1.1.3 Method 3: Synthesis from Halophosphines and Organometallic

Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12942.5.1.1.3.1 Variation 1: Synthesis from Dialkylhalophosphines and Dimetalated

Alkanes, Alkenes, or Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12942.5.1.1.3.2 Variation 2: Synthesis from Bis(halophosphino)alkanes and

Organometallic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13042.5.1.1.4 Method 4: Reduction of Phosphine Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13242.5.1.1.4.1 Variation 1: Reduction of Bis(dialkylphosphoryl)alkanes with Silanes . . . . . 13242.5.1.1.4.2 Variation 2: Reduction of Bis(dialkylphosphoryl)alkanes with Lithium

Aluminum Hydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13342.5.1.1.5 Method 5: Addition to Double Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13542.5.1.1.5.1 Variation 1: Addition of Phosphines to Polyenes and Their Heteroatom

Analogues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13542.5.1.1.5.2 Variation 2: Addition of Dialkylphosphines to Vinyl- or Allylphosphines . . . 13742.5.1.1.5.3 Variation 3: Addition of Polyphosphinoalkanes to C=C or C=X Bonds . . . . 13942.5.1.1.5.4 Variation 4: Addition of Diphosphines to Alkynes . . . . . . . . . . . . . . . . . . . . . . . . 14142.5.1.1.6 Method 6: Decomposition of Phosphonium Salts . . . . . . . . . . . . . . . . . . . . . . 14242.5.1.1.6.1 Variation 1: Reductive Cleavage of Quaternary Phosphonium Salts . . . . . . . 14242.5.1.1.6.2 Variation 2: Alcoholysis of Quaternary Phosphonium Salts . . . . . . . . . . . . . . . 14342.5.1.1.7 Method 7: Interconversion of Poly(alkylphosphino)alkanes . . . . . . . . . . . . . 14342.5.1.1.7.1 Variation 1: From Diphosphinomethanides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14342.5.1.1.8 Method 8: Di- and Oligomerization by Interaction of Functional

Groups of Phosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14442.5.1.1.8.1 Variation 1: Di- and Oligomerization of Phosphino Alcohols . . . . . . . . . . . . . . 144

42.5.2 Product Subclass 2: Tetraalkyldiphosphines and Polyalkylpolyphosphineswith a P—P Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145

42.5.2.1 Synthesis of Product Subclass 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146

42.5.2.1.1 Method 1: Synthesis from Dialkylphosphides or Dialkylphosphines andDialkylhalophosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146

42.5.2.1.2 Method 2: Coupling of Dialkylphosphine Derivatives . . . . . . . . . . . . . . . . . . . 14742.5.2.1.2.1 Variation 1: Oxidative Coupling of Dialkylphosphines by Transition-Metal

Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14742.5.2.1.2.2 Variation 2: Reductive Coupling of Dialkylhalophosphines by Alkali

Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14842.5.2.1.3 Method 3: Interconversion of Alkylpolyphosphines . . . . . . . . . . . . . . . . . . . . . 14842.5.2.1.3.1 Variation 1: Alkylation of Polyphosphide Anions . . . . . . . . . . . . . . . . . . . . . . . . . 14842.5.2.1.3.2 Variation 2: Insertion into P—P Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149

Table of Contents XV


42.6 Product Class 6: Cyclic PhosphinesD. Gudat

42.6 Product Class 6: Cyclic Phosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155

42.6.1 Product Subclass 1: Phosphiranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155


42.6.1.1.1 Method 1: P-Alkylation of Primary Phosphines . . . . . . . . . . . . . . . . . . . . . . . . . 15642.6.1.1.1.1 Variation 1: From Phosphines or Metal Phosphides and 1,2-Dihalides

or 1,2-Bis(toluenesulfonates) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15742.6.1.1.1.2 Variation 2: From Metal Phosphides and Oxiranes . . . . . . . . . . . . . . . . . . . . . . . 15942.6.1.1.2 Method 2: P-Alkylation of Dichlorophosphines . . . . . . . . . . . . . . . . . . . . . . . . . 16042.6.1.1.3 Method 3: Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16142.6.1.1.3.1 Variation 1: From Electrophilic Phosphinidene Complexes and Alkenes . . . 16142.6.1.1.3.2 Variation 2: From Phosphaalkenes and Diazoalkanes . . . . . . . . . . . . . . . . . . . . 16242.6.1.1.3.3 Variation 3: From Phosphaalkenes or Phosphacumulenes and Carbenes

or Carbenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16442.6.1.1.4 Methods 4: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166

42.6.2 Product Subclass 2: Phosphetanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166


42.6.2.1.1 Method 1: P-Alkylation of Primary Phosphines . . . . . . . . . . . . . . . . . . . . . . . . . 16742.6.2.1.1.1 Variation 1: From Phosphines and 1,3-Dihalides or Derivatives of 1,3-Diols 16742.6.2.1.1.2 Variation 2: From Phosphines and Cyclic Sulfates . . . . . . . . . . . . . . . . . . . . . . . . 16942.6.2.1.2 Method 2: P-Alkylation of Dichlorophosphines . . . . . . . . . . . . . . . . . . . . . . . . . 17142.6.2.1.2.1 Variation 1: Lewis Acid Induced Cyclization of Dichlorophosphines

with Alkenes and Subsequent Reduction . . . . . . . . . . . . . . . . . . . . 17142.6.2.1.2.2 Variation 2: P-Alkylation of Dichlorophosphines . . . . . . . . . . . . . . . . . . . . . . . . . 17342.6.2.1.3 Method 3: Transformation of Phosphetanes . . . . . . . . . . . . . . . . . . . . . . . . . . . 17342.6.2.1.3.1 Variation 1: P-Substitution of P-Halophosphetanes . . . . . . . . . . . . . . . . . . . . . . 17442.6.2.1.3.2 Variation 2: C-Substitution of Protected Phosphetanes and Subsequent

Deprotection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17442.6.2.1.4 Methods 4: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176

42.6.3 Product Subclass 3: 1,3-Diphosphetanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176


42.6.3.1.1 Method 1: Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17742.6.3.1.1.1 Variation 1: Cyclodimerization of Phosphaalkenes . . . . . . . . . . . . . . . . . . . . . . . 17742.6.3.1.1.2 Variation 2: Cyclooligomerization of Phosphaalkynes . . . . . . . . . . . . . . . . . . . . 17842.6.3.1.1.3 Variation 3: Oxidative Coupling of Polyphospholides . . . . . . . . . . . . . . . . . . . . 17942.6.3.1.2 Methods 2: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180

42.6.4 Product Subclass 4: Five- and Six-Membered Rings: Phospholanes,Phosphinanes, 2,5-Dihydrophospholes, and 1,2,5,6-Tetrahydro-phosphinines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180


42.6.4.1.1 Method 1: P-Alkylation of Primary Phosphines . . . . . . . . . . . . . . . . . . . . . . . . . 181

XVI Table of Contents


42.6.4.1.1.1 Variation 1: From Phosphines and a,w-Dihalides or Disulfonates ofa,w-Diols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181

42.6.4.1.1.2 Variation 2: From Phosphines and Cyclic Sulfates . . . . . . . . . . . . . . . . . . . . . . . . 18342.6.4.1.2 Method 2: Alkylation of Dichlorophosphines or Phosphinic Acid

O,S-Diesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18642.6.4.1.2.1 Variation 1: From Dichlorophosphines or Phosphinic Acid O,S-Diesters

and a,w-Di-Grignard or Dilithium Reagents . . . . . . . . . . . . . . . . . 18642.6.4.1.2.2 Variation 2: From Dichlorophosphines, Alkenes, and Organometallic

Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18742.6.4.1.3 Method 3: Hydrophosphination of Double Bonds . . . . . . . . . . . . . . . . . . . . . . 18842.6.4.1.3.1 Variation 1: Addition of Phosphines to Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . 18942.6.4.1.3.2 Variation 2: Addition of Phosphine and Primary Phosphines to

1,4-Dien-3-ones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19042.6.4.1.3.3 Variation 3: Addition of Phosphines to Carbonyl Compounds . . . . . . . . . . . . 19242.6.4.1.4 Method 4: Cycloaddition or Metathesis Reactions . . . . . . . . . . . . . . . . . . . . . . 19242.6.4.1.4.1 Variation 1: 2,5-Dihydrophospholes from Dihalophosphines and Dienes

via [4 + 1] Cycloaddition and Reduction . . . . . . . . . . . . . . . . . . . . . 19342.6.4.1.4.2 Variation 2: 1,2,5,6-Tetrahydrophosphinines from Phosphaalkenes and

1,3-Dienes via [4 + 2] Cycloaddition . . . . . . . . . . . . . . . . . . . . . . . . . 19542.6.4.1.4.3 Variation 3: 7-Phosphanorbornenes from [4 + 2] Cycloaddition of

Phosphole Derivatives with Dienophiles . . . . . . . . . . . . . . . . . . . . . 19642.6.4.1.4.4 Variation 4: 2,5-Dihydrophospholes from Diallylphosphines via Alkene

Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19942.6.4.1.5 Method 5: Transformation of Cyclic Phosphines . . . . . . . . . . . . . . . . . . . . . . . . 20042.6.4.1.5.1 Variation 1: Transformation of P-Substituents in Five- and Six-Membered

Heterocycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20042.6.4.1.5.2 Variation 2: Lithiation and Electrophilic Substitution at a-C—H Bonds

in Cyclic Phosphine Oxides and Borane Complexes . . . . . . . . . . 20142.6.4.1.6 Methods 6: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203

42.6.5 Product Subclass 5: Cyclic Phosphines with Seven-Membered andLarger Rings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204


42.6.5.1.1 Method 1: P-Alkylation of Phosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20542.6.5.1.2 Method 2: P-Alkylation of Dihalophosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . 20642.6.5.1.3 Method 3: P-Alkylation of Tertiary Phosphines or Diphosphines and

Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20742.6.5.1.4 Method 4: Hydrophosphination of Alkenes and Alkynes . . . . . . . . . . . . . . . . 21042.6.5.1.5 Methods 5: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212

42.7 Product Class 7: Dialkylphosphinous Acids and DerivativesK. M. Pietrusiewicz and M. Stankevič

42.7 Product Class 7: Dialkylphosphinous Acids and Derivatives . . . . . . . . . . . . . . 221

42.7.1 Product Subclass 1: Dialkylphosphinous Acid Halides . . . . . . . . . . . . . . . . . . . . 221


42.7.1.1.1 Method 1: Synthesis from Phosphorous Halides by P—C Bond Formation 221

Table of Contents XVII


42.7.1.1.2 Method 2: Ligand Exchange in Dialkylphosphinous Acid Derivatives . . . . . 222

42.7.1.2 Applications of Product Subclass 1 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . 223

42.7.2 Product Subclass 2: Dialkylphosphinous Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . 224


42.7.2.1.1 Method 1: Synthesis from H-Phosphonates by Substitution . . . . . . . . . . . . . 22442.7.2.1.2 Method 2: Hydrolysis of Dialkylphosphinous Acid Derivatives . . . . . . . . . . . 226


42.7.3 Product Subclass 3: Dialkylphosphinous Acid Esters . . . . . . . . . . . . . . . . . . . . . 227


42.7.3.1.1 Method 1: Alcoholysis of Dialkylphosphinous Acid Derivatives . . . . . . . . . . 22742.7.3.1.2 Method 2: Synthesis from Phosphorous Acid Monoester Dihalides by

P—C Bond Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228


42.7.4 Product Subclass 4: Dialkylthiophosphinous Acids . . . . . . . . . . . . . . . . . . . . . . . 230


42.7.4.1.1 Method 1: Synthesis from Dialkylphosphinous Acid Derivatives . . . . . . . . . 230


42.7.5 Product Subclass 5: Dialkylthiophosphinous Acid Esters . . . . . . . . . . . . . . . . . 231


42.7.5.1.1 Method 1: Synthesis from Dialkylphosphinous Acid Halides . . . . . . . . . . . . 231

42.7.6 Product Subclass 6: Dialkylselenophosphinous Acids . . . . . . . . . . . . . . . . . . . . . 231


42.7.6.1.1 Method 1: Synthesis from Dialkylphosphines . . . . . . . . . . . . . . . . . . . . . . . . . . 232

42.7.7 Product Subclass 7: Dialkylselenophosphinous Acid Esters . . . . . . . . . . . . . . . 232


42.7.7.1.1 Method 1: Synthesis from Dialkylphosphinous Acid Halides . . . . . . . . . . . . 232

42.7.8 Product Subclass 8: Dialkylphosphinous Acid Amides . . . . . . . . . . . . . . . . . . . . 233


42.7.8.1.1 Method 1: Aminolysis of Dialkylphosphinous Acid Derivatives . . . . . . . . . . 23342.7.8.1.2 Method 2: Synthesis from Phosphorous Acid Derivatives by P—C Bond

Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234


42.8 Product Class 8: Alkylphosphonous Acids and DerivativesK. M. Pietrusiewicz and M. Stankevič

42.8 Product Class 8: Alkylphosphonous Acids and Derivatives . . . . . . . . . . . . . . . . 243

42.8.1 Product Subclass 1: Alkylphosphonous Acid Dihalides . . . . . . . . . . . . . . . . . . . 243


XVIII Table of Contents


42.8.1.1.1 Method 1: Electrophilic Alkylation of Phosphorus Trihalides . . . . . . . . . . . . 24442.8.1.1.2 Method 2: Nucleophilic Alkylation of Phosphorus Trihalides by

Organometallic Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24442.8.1.1.3 Method 3: Ligand Exchange Using Alkylphosphines as Substrates . . . . . . . 245


42.8.2 Product Subclass 2: Alkylphosphonous Acid Monohalides . . . . . . . . . . . . . . . . 247


42.8.2.1.1 Method 1: Partial Hydrolysis of Alkyl(dihalo)phosphines . . . . . . . . . . . . . . . . 247

42.8.3 Product Subclass 3: Alkylphosphonous Acid Monoester Monohalides . . . . 247


42.8.3.1.1 Method 1: Ligand Exchange in Alkyl(dihalo)phosphines . . . . . . . . . . . . . . . . 247

42.8.4 Product Subclass 4: Alkylthiophosphonous Acid Monohalide Monoesters 248


42.8.4.1.1 Method 1: Ligand Exchange of Alkyl(dihalo)phosphines . . . . . . . . . . . . . . . . 248

42.8.5 Product Subclass 5: Alkylphosphonous Acid Monoamide Monohalides . . . 249


42.8.5.1.1 Method 1: Partial Aminolysis of Alkyl(dihalo)phosphines . . . . . . . . . . . . . . . 24942.8.5.1.2 Method 2: Ligand Exchange in Alkyl(amino)phosphine Derivatives . . . . . . 250

42.8.6 Product Subclass 6: Alkylphosphonous Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251


42.8.6.1.1 Method 1: Hydrolysis of Alkyl(halo)phosphines . . . . . . . . . . . . . . . . . . . . . . . . 25142.8.6.1.2 Method 2: Hydrophosphination of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252


42.8.7 Product Subclass 7: Alkylphosphonous Acid Monoesters . . . . . . . . . . . . . . . . . 253


42.8.7.1.1 Method 1: Alcoholysis of Alkylphosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25342.8.7.1.2 Method 2: Esterification of Monoalkylphosphinic Acids . . . . . . . . . . . . . . . . . 25442.8.7.1.3 Method 3: Hydrolysis of Dialkyl Phosphonites and Related Compounds . 25542.8.7.1.4 Method 4: Hydrophosphination of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255


42.8.8 Product Subclass 8: Alkylphosphonous Acid Diesters . . . . . . . . . . . . . . . . . . . . . 256


42.8.8.1.1 Method 1: Alcoholysis of Alkylphosphonites . . . . . . . . . . . . . . . . . . . . . . . . . . . 25642.8.8.1.2 Method 2: Synthesis from Halophosphonites . . . . . . . . . . . . . . . . . . . . . . . . . . 257


42.8.9 Product Subclass 9: Alkylthiophosphonous Acid S-Monoesters . . . . . . . . . . . 258


42.8.9.1.1 Method 1: Hydrolysis of Alkyl(alkylsulfanyl)(halo)phosphines . . . . . . . . . . . 258

42.8.10 Product Subclass 10: Alkylphosphonous Acid Monoamides . . . . . . . . . . . . . . 259

Table of Contents XIX


42.8.10.1 Synthesis of Product Subclass 10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259

42.8.10.1.1 Method 1: Hydrolysis of Alkyl(diamino)phosphines . . . . . . . . . . . . . . . . . . . . . 259

42.8.11 Product Subclass 11: Alkylthiophosphonous Acid O-Monoesters . . . . . . . . . 259


42.8.11.1.1 Method 1: Synthesis from Alkyl(alkoxy)(halo)phosphines . . . . . . . . . . . . . . . 260

42.8.12 Product Subclass 12: Alkylthiophosphonous Acid Diesters . . . . . . . . . . . . . . . 260


42.8.12.1.1 Method 1: Alcoholysis of Alkyl(alkylsulfanyl)(halo)phosphines . . . . . . . . . . 260

42.8.13 Product Subclass 13: Alkylphosphonous Acid Monoester Monoamides . . . 261


42.8.13.1.1 Method 1: Alcoholysis of Alkylphosphine Derivatives . . . . . . . . . . . . . . . . . . . 26142.8.13.1.2 Method 2: Aminolysis of Alkylphosphonous Acid Derivatives . . . . . . . . . . . 262

42.8.13.2 Applications of Product Subclass 13 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 262

42.8.14 Product Subclass 14: Alkyldithiophosphonous Acid Diesters . . . . . . . . . . . . . 263


42.8.14.1.1 Method 1: Synthesis from Primary Alkylphosphines and Disulfides . . . . . . 26342.8.14.1.2 Method 2: Thioalcoholysis of Alkyl(dihalo)phosphines . . . . . . . . . . . . . . . . . . 263

42.8.15 Product Subclass 15: Alkylthiophosphonous Acid Monoester Monoamides 264


42.8.15.1.1 Method 1: Thioalcoholysis of Alkyl(diamino)phosphines . . . . . . . . . . . . . . . . 264

42.8.16 Product Subclass 16: Alkyldiselenophosphonous Acid Diesters . . . . . . . . . . . 265


42.8.16.1.1 Method 1: Selenoalcoholysis of Alkyl(dihalo)phosphines . . . . . . . . . . . . . . . 265

42.8.17 Product Subclass 17: Alkylphosphonous Acid Diamides . . . . . . . . . . . . . . . . . . 265


42.8.17.1.1 Method 1: Aminolysis of Substituted Alkylphosphines . . . . . . . . . . . . . . . . . . 26542.8.17.1.2 Method 2: Synthesis from Diamino(halo)phosphines . . . . . . . . . . . . . . . . . . . 266


42.9 Product Class 9: Phosphorous Acid and DerivativesM. Stankevič and K. M. Pietrusiewicz

42.9 Product Class 9: Phosphorous Acid and Derivatives . . . . . . . . . . . . . . . . . . . . . . 275

42.9.1 Product Subclass 1: Phosphorous Acid Monoester Dihalides . . . . . . . . . . . . . 275


42.9.1.1.1 Method 1: Alcoholysis of Phosphorus Trihalides . . . . . . . . . . . . . . . . . . . . . . . . 27542.9.1.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives . 276


42.9.2 Product Subclass 2: Phosphorothious Acid S-Monoester Dihalides . . . . . . . 276

XX Table of Contents



42.9.2.1.1 Method 1: Thioalcoholysis of Phosphorus Trihalides . . . . . . . . . . . . . . . . . . . . 277


42.9.3 Product Subclass 3: Phosphorous Acid Monoamide Dihalides . . . . . . . . . . . . 277


42.9.3.1.1 Method 1: Aminolysis of Phosphorus Trihalides . . . . . . . . . . . . . . . . . . . . . . . . 27742.9.3.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives . 278


42.9.4 Product Subclass 4: Phosphorous Acid Monoester Monohalides . . . . . . . . . . 279

42.9.5 Product Subclass 5: Phosphorous Acid Diester Monohalides . . . . . . . . . . . . . 279


42.9.5.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . 28042.9.5.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives . 280


42.9.6 Product Subclass 6: Phosphorothious Acid Diester Monohalides . . . . . . . . . 282


42.9.6.1.1 Method 1: Amine–Halogen Exchange in Phosphorothious Acid DiesterMonoamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282

42.9.7 Product Subclass 7: Phosphorous Acid Monoester Monoamide Monoha-lides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282


42.9.7.1.1 Method 1: Alcoholysis of Phosphorous Acid Monoamide Dihalides . . . . . . 28342.9.7.1.2 Method 2: Aminolysis of Phosphorous Acid Monoester Dihalides . . . . . . . 28342.9.7.1.3 Method 3: Consecutive Alcoholysis and Aminolysis of Phosphorus

Trihalides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28342.9.7.1.4 Method 4: Ligand-Exchange Reactions of Phosphorous Acid Derivatives . 284


42.9.8 Product Subclass 8: Phosphorodithious Acid Diester Monohalides . . . . . . . 285


42.9.8.1.1 Method 1: Thioalcoholysis of Phosphorus Trihalides . . . . . . . . . . . . . . . . . . . . 28542.9.8.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives . 285

42.9.9 Product Subclass 9: Phosphorothious Acid Monoester MonoamideMonohalides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286


42.9.9.1.1 Method 1: Amine–Halogen Exchange in Phosphorothious Acid DiesterMonoamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286

42.9.10 Product Subclass 10: Phosphorous Acid Diamide Monohalides . . . . . . . . . . . 287


42.9.10.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . . 28742.9.10.1.2 Method 2: Ligand-Exchange Reactions of Phosphorous Acid Derivatives . 288

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42.9.11 Product Subclass 11: Phosphorous Acid Monoesters . . . . . . . . . . . . . . . . . . . . . 288


42.9.11.1.1 Method 1: Hydrolysis of Phosphorous Acid Esters . . . . . . . . . . . . . . . . . . . . . . 28942.9.11.1.2 Method 2: Synthesis from Other Phosphorous Acid Derivatives . . . . . . . . . 28942.9.11.1.3 Method 3: Esterification of Phosphorous Acid . . . . . . . . . . . . . . . . . . . . . . . . . . 290


42.9.12 Product Subclass 12: Phosphorous Acid Diesters (Secondary Phosphites) 291


42.9.12.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . . 29142.9.12.1.2 Method 2: Alcoholysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . 29242.9.12.1.3 Method 3: Other Syntheses from Phosphorous Acid Derivatives . . . . . . . . 29342.9.12.1.4 Method 4: Esterification of Phosphorous Acid Derivatives . . . . . . . . . . . . . . 293


42.9.13 Product Subclass 13: Phosphorous Acid Triesters (Tertiary Phosphites) . . . 295


42.9.13.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . 29542.9.13.1.2 Method 2: Transesterification of Phosphorous Acid Triesters . . . . . . . . . . . . 297


42.9.14 Product Subclass 14: Phosphorothious Acid O-Monoesters . . . . . . . . . . . . . . . 298


42.9.14.1.1 Method 1: Sulfanylation of Phosphorous Acid Diesters . . . . . . . . . . . . . . . . . 298

42.9.15 Product Subclass 15: Phosphorothious Acid O,O-Diesters . . . . . . . . . . . . . . . . 299


42.9.15.1.1 Method 1: Sulfanylation of Phosphorous Acid Derivatives . . . . . . . . . . . . . . 299


42.9.16 Product Subclass 16: Phosphorothious Acid Triesters . . . . . . . . . . . . . . . . . . . . 300


42.9.16.1.1 Method 1: Alcoholysis of Phosphorothious Acid Derivatives . . . . . . . . . . . . 30042.9.16.1.2 Method 2: Thioalcoholysis of Phosphorous Acid Derivatives . . . . . . . . . . . . 301

42.9.17 Product Subclass 17: Phosphorodithious Acid S,S-Diesters . . . . . . . . . . . . . . . 301

42.9.18 Product Subclass 18: Phosphorodithious Acid O-Monoesters . . . . . . . . . . . . . 301

42.9.19 Product Subclass 19: Phosphorodithious Acid Triesters . . . . . . . . . . . . . . . . . . 302


42.9.19.1.1 Method 1: Thioalcoholysis of Phosphorous Acid Derivatives . . . . . . . . . . . . 302

42.9.20 Product Subclass 20: Phosphoroselenous Acid O,O-Diesters . . . . . . . . . . . . . . 303


42.9.20.1.1 Method 1: Selanylation of Phosphorous Acid Diester Monohalides . . . . . . 303

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42.9.21 Product Subclass 21: Phosphorous Acid Monoester Monoamides . . . . . . . . 303


42.9.21.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . . 303

42.9.22 Product Subclass 22: Phosphorous Acid Diester Monoamides . . . . . . . . . . . . 304


42.9.22.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . 30442.9.22.1.2 Method 2: Aminolysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . . 306


42.9.23 Product Subclass 23: Phosphorothious Acid Diester Monoamides . . . . . . . . 307



42.9.24 Product Subclass 24: Phosphorous Acid Diamides . . . . . . . . . . . . . . . . . . . . . . . . 308


42.9.24.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . . 308

42.9.25 Product Subclass 25: Phosphorous Acid Monoester Diamides . . . . . . . . . . . . 309


42.9.25.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . 30942.9.25.1.2 Method 2: Aminolysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . . 310


42.9.26 Product Subclass 26: Phosphorotrithious Acid Triesters . . . . . . . . . . . . . . . . . . 311



42.9.27 Product Subclass 27: Phosphorodithious Acid Diester Monoamides . . . . . . 312


42.9.27.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . . 312

42.9.28 Product Subclass 28: Phosphorothious Acid Monoester Diamides . . . . . . . . 312



42.9.29 Product Subclass 29: Phosphorotriselenous Acid Triesters . . . . . . . . . . . . . . . 313


42.9.29.1.1 Method 1: Reaction of a Diselenide with Elemental Phosphorus . . . . . . . . . 313

42.9.30 Product Subclass 30: Phosphorous Acid Triamides . . . . . . . . . . . . . . . . . . . . . . . 313


42.9.30.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives . . . . . . . . . . . . . . . . . 314


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42.10 Applications of Tricoordinated Phosphorus Compoundsin Homogeneous Catalysis

42.10.1 General Catalytic MethodsM. Toffano

42.10.1 General Catalytic Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347

42.10.1.1 Formation of C—C Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347

42.10.1.1.1 Method 1: Palladium-Promoted Cross-Coupling Reactions . . . . . . . . . . . . . . 34742.10.1.1.2 Method 2: Catalysis with Phosphonium Salts as Ligand Precursors . . . . . . 352

42.10.1.2 Formation of C—N Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353

42.10.1.2.1 Method 1: Amination of Aryl and Hetaryl Halides orTrifluoromethanesulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353

42.10.1.2.2 Method 2: Amination of Alk-1-enyl Halides orTrifluoromethanesulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360

42.10.1.2.3 Method 3: Intramolecular Amination Reactions . . . . . . . . . . . . . . . . . . . . . . . . 360

42.10.1.3 Formation of C—O Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361

42.10.1.3.1 Method 1: Alkyl Aryl Ether Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36142.10.1.3.2 Method 2: Diaryl Ether Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362

42.10.1.4 Formation of C—P Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363

42.10.1.4.1 Method 1: Formation of Alkylphosphorus Compounds . . . . . . . . . . . . . . . . . 36342.10.1.4.2 Method 2: Formation of Alkenylphosphorus Compounds . . . . . . . . . . . . . . . 36442.10.1.4.2.1 Variation 1: Hydrophosphination of Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36442.10.1.4.2.2 Variation 2: Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36642.10.1.4.3 Method 3: Formation of Alkynylphosphorus Compounds . . . . . . . . . . . . . . . 36842.10.1.4.4 Method 4: Formation of Arylphosphorus Compounds . . . . . . . . . . . . . . . . . . 368

42.10.1.5 Formation of C—S Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369

42.10.1.5.1 Method 1: Formation of an Aryl—Sulfur Bond . . . . . . . . . . . . . . . . . . . . . . . . . . 37042.10.1.5.2 Method 2: Formation of an Alkenyl—Sulfur Bond . . . . . . . . . . . . . . . . . . . . . . . 37042.10.1.5.3 Method 3: Formation of an Alkynyl—Sulfur Bond . . . . . . . . . . . . . . . . . . . . . . . 371

42.10.1.6 Formation of C—Sn Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372

42.10.1.7 Synthesis with Catalyst Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373

42.10.1.7.1 Method 1: Catalysis with Fluorinated Phosphines . . . . . . . . . . . . . . . . . . . . . . 37342.10.1.7.2 Method 2: Catalysis with Water-Soluble Phosphines . . . . . . . . . . . . . . . . . . . . 37442.10.1.7.2.1 Variation 1: Catalysis with Sulfonated and Carboxylated Phosphines . . . . . 37542.10.1.7.2.2 Variation 2: Catalysis with Phosphines Bearing Ammonium Groups . . . . . . 37642.10.1.7.2.3 Variation 3: Catalysis with Carbohydrate-Derived Phosphines . . . . . . . . . . . . 37742.10.1.7.2.4 Variation 4: Catalysis with Polyether Phosphines . . . . . . . . . . . . . . . . . . . . . . . . 37742.10.1.7.3 Method 3: Catalysis with Polymer-Supported Phosphines . . . . . . . . . . . . . . 37842.10.1.7.3.1 Variation 1: Metal-Promoted Catalysis with Polymer-Supported

Phosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37842.10.1.7.3.2 Variation 2: Catalysis with Polymer-Supported Phosphine Reagents . . . . . . 380

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42.10.2 Enantioselective Catalytic MethodsJ.-C. Fiaud and A. Marinetti

42.10.2 Enantioselective Catalytic Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391

42.10.2.1 Approaches to Enantioselective Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391

42.10.2.1.1 Method 1: Approaches to Chiral Cyclic Phosphines . . . . . . . . . . . . . . . . . . . . . 39742.10.2.1.1.1 Variation 1: Phospholane-Based Chiral Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . 39742.10.2.1.1.2 Variation 2: Phosphetane-Based Chiral Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . 39842.10.2.1.1.3 Variation 3: Phosphepin-Based Chiral Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . 39942.10.2.1.2 Method 2: Approaches to Atropisomeric Biaryl Bisphosphines . . . . . . . . . . 39942.10.2.1.3 Method 3: Approaches to Ferrocenylphosphines with Planar Chirality . . . 40242.10.2.1.4 Method 4: Approaches to Hybrid Phosphorus–Nitrogen Ligands . . . . . . . . 40542.10.2.1.4.1 Variation 1: Phosphino-4,5-dihydrooxazole Ligands . . . . . . . . . . . . . . . . . . . . . 40542.10.2.1.4.2 Variation 2: Phosphinite–4,5-Dihydrooxazole Ligands . . . . . . . . . . . . . . . . . . . 40842.10.2.1.4.3 Variation 3: Phosphino-4,5-dihydro-1H-imidazole Ligands . . . . . . . . . . . . . . . 40842.10.2.1.4.4 Variation 4: Phosphinopyridine and Phosphinoquinoline Ligands . . . . . . . . . 40842.10.2.1.4.5 Variation 5: Pyridylphosphinite and Quinolylphosphinite Ligands . . . . . . . . . 40942.10.2.1.4.6 Variation 6: Trost Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40942.10.2.1.5 Method 5: Approaches to Ligands Bearing P—O and P—N Bonds . . . . . . . . 41042.10.2.1.5.1 Variation 1: Phosphinite [P(C,C,O)] Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41042.10.2.1.5.2 Variation 2: Phosphonite [P(C,O,O)] Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41042.10.2.1.5.3 Variation 3: Phosphite [P(O,O,O)] Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41042.10.2.1.5.4 Variation 4: Phosphoramidite [P(O,O,N)] Ligands . . . . . . . . . . . . . . . . . . . . . . . 410

42.10.2.2 Enantioselective C—C Bond-Forming Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411

42.10.2.2.1 Method 1: Metal-Catalyzed Allylic Alkylation (Tsuji–Trost Reaction) . . . . . 41142.10.2.2.1.1 Variation 1: Using 1,3-Symmetrically Substituted Allylic Ligands . . . . . . . . . 41142.10.2.2.1.2 Variation 2: Using Monosubstituted Allylic Ligands . . . . . . . . . . . . . . . . . . . . . . 41342.10.2.2.1.3 Variation 3: Using 1,3-Dissymmetrically Disubstituted Allylic Substrates . . 41542.10.2.2.2 Method 2: Palladium-Catalyzed Arylation of Alkenes (Heck Reaction) . . . 41842.10.2.2.2.1 Variation 1: Selection of Enantiotopic C=C Bonds of an Achiral Substrate . 41942.10.2.2.2.2 Variation 2: Selection of Enantiotopic Faces of an Achiral Alkenic Substrate 42042.10.2.2.2.3 Variation 3: Selection of Enantiotopic Sites of an Achiral Alkenic Substrate 42342.10.2.2.3 Method 3: Metal-Catalyzed Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . 42442.10.2.2.4 Method 4: Conjugate Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42742.10.2.2.4.1 Variation 1: Metal-Catalyzed 1,4-Addition of Organometallic Reagents to

Activated Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42742.10.2.2.4.2 Variation 2: Copper-Catalyzed Asymmetric 1,4-Addition of Organozinc

Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42742.10.2.2.4.3 Variation 3: Conjugate Addition to Cyclohexa-2,5-dienones . . . . . . . . . . . . . . 42842.10.2.2.4.4 Variation 4: Copper-Catalyzed Asymmetric 1,4-Addition of Grignard

Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42942.10.2.2.4.5 Variation 5: Rhodium-Catalyzed Asymmetric 1,4-Addition of Organoboron

Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42942.10.2.2.5 Methods 5: Miscellaneous Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43142.10.2.2.5.1 Variation 1: Metal-Catalyzed Addition of Organometallic Reagents to

Unactivated Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431

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42.10.2.2.5.2 Variation 2: Metal-Catalyzed Addition of Organometallic Reagentsto Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432

42.10.2.3 Enantioselective C—H Bond-Forming Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433

42.10.2.3.1 Method 1: Rhodium-Promoted Hydrogenation of Alkenes . . . . . . . . . . . . . . 43342.10.2.3.2 Method 2: Iridium-Promoted Hydrogenation of Nonfunctionalized

Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43842.10.2.3.3 Method 3: Iridium-Promoted Hydrogenation of Imines . . . . . . . . . . . . . . . . . 44142.10.2.3.4 Method 4: Ruthenium-Promoted Hydrogenation of Ketones . . . . . . . . . . . . 44442.10.2.3.5 Method 5: Rhodium-Promoted Hydroformylation of Alkenes . . . . . . . . . . . 45142.10.2.3.6 Method 6: Rhodium-Promoted Hydroboration of Alkenes . . . . . . . . . . . . . . 454

42.11 Applications of Tricoordinated Phosphorus Compounds inOrganocatalysisJ. L. Methot and W. R. Roush

42.11 Applications of Tricoordinated Phosphorus Compounds inOrganocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469

42.11.1 Method 1: Morita–Baylis–Hillman Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 46942.11.1.1 Variation 1: Tandem Phosphorylsilylation/Ireland–Claisen Rearrangement 47242.11.1.2 Variation 2: Intramolecular Morita–Baylis–Hillman Allylic Alkylation . . . . . . 47342.11.1.3 Variation 3: a-Arylation of Enones with Hypervalent Bismuth Reagents . . 47442.11.1.4 Variation 4: Phosphine-Mediated Reductive Condensation of

Acyloxybutynoates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47442.11.1.5 Variation 5: Regioselective Allylic Displacement . . . . . . . . . . . . . . . . . . . . . . . . . 47542.11.1.6 Variation 6: The Morita–Baylis–Hillman Reaction Using Air-Stable

Phosphine Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47642.11.1.7 Variation 7: Asymmetric Morita–Baylis–Hillman Reactions . . . . . . . . . . . . . . . 47642.11.1.8 Variation 8: The Aza-Morita–Baylis–Hillman Reaction . . . . . . . . . . . . . . . . . . . . 47742.11.2 Method 2: Michael Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47942.11.3 Method 3: Nucleophilic Addition Reactions at Nonactivated Positions . . . 48142.11.3.1 Variation 1: Chiral Nucleophilic Addition Reactions . . . . . . . . . . . . . . . . . . . . . . 48442.11.3.2 Variation 2: Nucleophilic Interception at the a-Position . . . . . . . . . . . . . . . . . 48542.11.3.3 Variation 3: Tandem a- or g-Addition and Michael Addition Reactions . . . . 48642.11.4 Method 4: [3 + 2]-Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48742.11.5 Method 5: [4 + 2]-Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49242.11.6 Method 6: Acylation and Kinetic Resolution of Alcohols . . . . . . . . . . . . . . . . 49542.11.7 Method 7: Isomerization of Activated Alkynes to Dienes . . . . . . . . . . . . . . . 497

42.12 Product Class 12: Alkylphosphonium SaltsD. Virieux, J.-N. Volle, and J.-L. Pirat

42.12 Product Class 12: Alkylphosphonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503

42.12.1 Product Subclass 1: Non-Heteroatom-SubstitutedAlkylphosphonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503


42.12.1.1.1 Method 1: Alkylation of Phosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50342.12.1.1.1.1 Variation 1: Alkylation of Tertiary Phosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . 503

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42.12.1.1.1.2 Variation 2: Alkylation of Tertiary Phosphines Using Alcohols or Derivatives 50442.12.1.1.1.3 Variation 3: Successive Alkylation of Phosphines, Phosphides, or

Polyphosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50542.12.1.1.1.4 Variation 4: Nucleophilic Addition of Phosphines or Derivatives

to Alkenes or Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50542.12.1.1.2 Method 2: Modification of Phosphonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . 50742.12.1.1.2.1 Variation 1: Diels–Alder Reaction of Triphenyl(vinyl)phosphonium Salts

with 1,4-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50742.12.1.1.2.2 Variation 2: Modification of Phosphonium Salts by Reaction of Ylides . . . . 50742.12.1.1.3 Method 3: Reaction of Phosphaalkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508

42.12.2 Product Subclass 2: Hydroxyphosphonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . 509


42.12.2.1.1 Method 1: Synthesis of a-Hydroxyphosphonium Salts and Derivatives . . 50942.12.2.1.1.1 Variation 1: Addition of Phosphines to Aldehydes or Ketones . . . . . . . . . . . . 50942.12.2.1.1.2 Variation 2: Alkylation of (a-Hydroxyalkyl)phosphines or Derivatives . . . . . 51142.12.2.1.1.3 Variation 3: Reaction of Phosphines with Acetals, Ketals, or Hemiacetals . 51342.12.2.1.1.4 Variation 4: Reaction of Phosphines with Enol Ethers . . . . . . . . . . . . . . . . . . . . 51342.12.2.1.2 Method 2: Synthesis of b-Hydroxyphosphonium Salts and Derivatives . . . 51442.12.2.1.2.1 Variation 1: Alkylation of Phosphines with b-Hydroxyalkyl Halides or

Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51442.12.2.1.2.2 Variation 2: Alkylation of (b-Hydroxyalkyl)phosphines or Derivatives . . . . . 51742.12.2.1.2.3 Variation 3: Reaction of Phosphines with Epoxides . . . . . . . . . . . . . . . . . . . . . . 52042.12.2.1.2.4 Variation 4: Reaction of Ylides with Ketones or Aldehydes . . . . . . . . . . . . . . . 52242.12.2.1.2.5 Variation 5: Transformation of b-Functionalized Phosphonium Salts . . . . . . 52442.12.2.1.3 Method 3: Synthesis of g-Hydroxyphosphonium Salts and Derivatives . . . 52642.12.2.1.3.1 Variation 1: Alkylation of Phosphines with g-Hydroxyalkyl Halides or

Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52642.12.2.1.3.2 Variation 2: Alkylation of g-Hydroxyphosphines and Derivatives with

Alkyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52842.12.2.1.3.3 Variation 3: Reaction of Ylides with Epoxides and 3-Oxaalkyl Halides . . . . . 52942.12.2.1.3.4 Variation 4: Transformation of g-Functionalized Phosphonium Salts . . . . . . 530

42.12.3 Product Subclass 3: Sulfanyl- and Selanylphosphonium Saltsand Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 531


42.12.3.1.1 Method 1: Synthesis of a-Sulfanyl and a-Selanylphosphonium Salts andDerivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 531

42.12.3.1.1.1 Variation 1: Alkylation of Phosphines with Sulfur- or Selenium-SubstitutedAlkyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 531

42.12.3.1.1.2 Variation 2: Alkylation of Phosphines with Bis(sulfanyl)- or Bis(selanyl)Alkyl Halides, or Cationic Derivatives . . . . . . . . . . . . . . . . . . . . . . . 533

42.12.3.1.1.3 Variation 3: Transformation of Phosphonium Salts with Anionic SulfurNucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535

42.12.3.1.1.4 Variation 4: Reaction of Ylides with Sulfur- or Selenium-ContainingElectrophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536

42.12.3.1.2 Method 2: Synthesis of b-Sulfanyl- and b-Selanylphosphonium Saltsand Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 537

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42.12.3.1.2.1 Variation 1: Alkylation of Phosphines with Sulfur- or Selenium-ContainingAlkyl Halides or Sulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538

42.12.3.1.2.2 Variation 2: Reaction of Phosphines with 1,1,2-Trimethyldisulfaniumor 1-Methyl-1,2-diphenyldisulfanium Salts . . . . . . . . . . . . . . . . . . 539

42.12.3.1.2.3 Variation 3: Reaction of Vinylphosphonium Salts with Sulfur Dioxide,Thiols, or Associated Anions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 540

42.12.3.1.2.4 Variation 4: Reaction of Ylides with Miscellaneous Electrophiles . . . . . . . . . . 54242.12.3.1.3 Method 3: Synthesis of g-Sulfanyl- and g-Selanylphosphonium Salts

and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54342.12.3.1.3.1 Variation 1: Alkylation of Phosphines with Sulfur- or Selenium-Substituted

Alkyl Halides or Related Compounds . . . . . . . . . . . . . . . . . . . . . . . . 54342.12.3.1.3.2 Variation 2: Transformation of Phosphonium Salts . . . . . . . . . . . . . . . . . . . . . . 544

42.12.4 Product Subclass 4: Carbonylphosphonium Salts and Derivatives . . . . . . . . 545


42.12.4.1.1 Method 1: Synthesis of P-Carbonylphosphonium Salts and Derivatives . . 54542.12.4.1.1.1 Variation 1: Reaction of Phosphines with Various Carbonyl Electrophiles . . 54642.12.4.1.1.2 Variation 2: Alkylation of P-Carbonylphosphines with Alkyl Halides or

Sulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54842.12.4.1.2 Method 2: Synthesis of a-Carbonylphosphonium Salts and Derivatives . . 55042.12.4.1.2.1 Variation 1: Alkylation of Phosphines with a-(Halomethyl)carbonyl Species 55042.12.4.1.2.2 Variation 2: Reaction of Ylides with Carbonylated Electrophiles . . . . . . . . . . 55342.12.4.1.2.3 Variation 3: Reaction of Stabilized Ylides with Other Electrophiles . . . . . . . . 55642.12.4.1.2.4 Variations 4: Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55742.12.4.1.3 Method 3: Synthesis of b-Carbonyl-Substituted Phosphonium Salts and

Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55842.12.4.1.3.1 Variation 1: Alkylation of Phosphines with b-Carbonyl-Substituted Alkyl

Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55942.12.4.1.3.2 Variation 2: Reaction of Phosphines with a,b-Unsaturated Carbonyl

Species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56142.12.4.1.3.3 Variation 3: Alkylation of b-Carbonylphosphines with Alkyl Halides . . . . . . . 565

42.12.5 Product Subclass 5: Polyphosphonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 565


42.12.5.1.1 Method 1: Synthesis of Multiphosphonium Salts . . . . . . . . . . . . . . . . . . . . . . . 56642.12.5.1.1.1 Variation 1: Reaction with Multihalides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56642.12.5.1.1.2 Variation 2: Reaction of Unsaturated Precursors . . . . . . . . . . . . . . . . . . . . . . . . 56642.12.5.1.1.3 Variation 3: Recursive Synthesis from a Phosphine . . . . . . . . . . . . . . . . . . . . . . 56742.12.5.1.2 Method 2: Synthesis of Polymeric Phosphonium Salts . . . . . . . . . . . . . . . . . . 56742.12.5.1.2.1 Variation 1: Reaction of Phosphonium Monomers . . . . . . . . . . . . . . . . . . . . . . . 56742.12.5.1.2.2 Variation 2: Functionalization of Polymeric Backbones . . . . . . . . . . . . . . . . . . . 569

42.12.6 Product Subclass 6: Cyclic Phosphonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . 570


42.12.6.1.1 Method 1: Cyclization onto Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57042.12.6.1.1.1 Variation 1: Reaction of Secondary Phosphines or Derivatives with

1,n-Dielectrophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57042.12.6.1.1.2 Variation 2: Intramolecular Cyclization of Tertiary Phosphines . . . . . . . . . . . 571

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42.12.6.1.1.3 Variation 3: Intermolecular Cyclization of Tertiary Phosphines . . . . . . . . . . . 57242.12.6.1.1.4 Variation 4: Reaction of Halophosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57442.12.6.1.1.5 Variation 5: Reaction of Methylenephosphonium Ions . . . . . . . . . . . . . . . . . . . 57542.12.6.1.2 Method 2: Cyclization between Two Phosphorus Substituents . . . . . . . . . . 576

42.12.7 Product Subclass 7: Heterophosphonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . 577


42.12.7.1.1 Method 1: Synthesis from Tricoordinate Phosphorus Compounds . . . . . . . 57742.12.7.1.1.1 Variation 1: Alkylation of Tricoordinate Reagents . . . . . . . . . . . . . . . . . . . . . . . . 57742.12.7.1.1.2 Variation 2: Reaction of Phosphines with Heteroatomic Electrophiles . . . . 58042.12.7.1.2 Method 2: Synthesis from Tetracoordinate Phosphorus Compounds . . . . 58142.12.7.1.2.1 Variation 1: Modification of Heterophosphonium Salts . . . . . . . . . . . . . . . . . . 58142.12.7.1.2.2 Variation 2: Reaction of Electrophiles with Tetracoordinate Phosphorus

Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58242.12.7.1.2.3 Variation 3: Reaction of Secondary Phosphine–Borane Complexes . . . . . . . 582

42.13 Product Class 13: Trialkylphosphine Oxides, Sulfides, Selenides, Tellurides,and ImidesN. L. Kilah and S. B. Wild

42.13 Product Class 13: Trialkylphosphine Oxides, Sulfides, Selenides, Tellurides,and Imides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595

42.13.1 Product Subclass 1: Trialkylphosphine Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595


42.13.1.1.1 Method 1: Oxidation of Trialkylphosphines . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59542.13.1.1.1.1 Variation 1: Oxidation with Hydrogen Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . 59542.13.1.1.1.2 Variation 2: Oxidation with Sulfur(VI) Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59642.13.1.1.1.3 Variation 3: Oxidation by Nitrous Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59742.13.1.1.1.4 Variation 4: Oxidation with an Iodosylaryl Sulfone . . . . . . . . . . . . . . . . . . . . . . . 59742.13.1.1.2 Method 2: Oxidation of Phosphonium Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59842.13.1.1.3 Method 3: Addition of Dialkylphosphine Oxides to Alkenes . . . . . . . . . . . . . 59942.13.1.1.4 Method 4: Addition of Dialkylphosphine Oxides to Ketones or Aldehydes 60042.13.1.1.5 Method 5: Reactions of Dialkylphosphine Oxides with Alkyl Halides . . . . . 60242.13.1.1.5.1 Variation 1: Base-Induced Ionization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60242.13.1.1.5.2 Variation 2: Lewis Acid Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60342.13.1.1.5.3 Variation 3: Reduction with Sodium Bis(2-methoxyethoxy)aluminum

Hydride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60442.13.1.1.6 Method 6: Additions of Dialkyl(chloro)phosphines to Enones . . . . . . . . . . . 60542.13.1.1.7 Method 7: Reactions of Chlorophosphine Oxides with Grignard Reagents 60642.13.1.1.8 Method 8: Reactions of Dialkylphosphinites with Alkyl Halides . . . . . . . . . . 60742.13.1.1.9 Method 9: Isomerization of Dialkylphosphinites . . . . . . . . . . . . . . . . . . . . . . . . 60942.13.1.1.10 Method 10: Cycloaddition of Alkyl(dichloro)phosphines with Dienes . . . . . 61042.13.1.1.11 Method 11: Addition of Dialkylphosphine Oxides to Imines . . . . . . . . . . . . . . 61242.13.1.1.12 Method 12: Hydrogenation of Tertiary Arylphosphine Oxides . . . . . . . . . . . . 61242.13.1.1.13 Method 13: Conversion of Trialkylphosphine Ylides into Trialkylphosphine

Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61442.13.1.1.14 Method 14: Oxygenation of Trialkylphosphine Imides . . . . . . . . . . . . . . . . . . . 615

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42.13.1.1.14.1 Variation 1: By Reaction with a Ketone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61542.13.1.1.14.2 Variation 2: By Reaction with Methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61542.13.1.1.14.3 Variation 3: By Treatment with an Oxidizing Agent . . . . . . . . . . . . . . . . . . . . . . 61642.13.1.1.15 Method 15: Oxygenation of Trialkylphosphine Sulfides . . . . . . . . . . . . . . . . . . 61642.13.1.1.15.1 Variation 1: Treatment with Phosgene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61642.13.1.1.15.2 Variation 2: Treatment with Dimethyldioxirane . . . . . . . . . . . . . . . . . . . . . . . . . . 61742.13.1.1.15.3 Variation 3: Treatment with Trifluoroacetic Anhydride . . . . . . . . . . . . . . . . . . . 61742.13.1.1.15.4 Variation 4: Treatment with 7-Oxabicyclo[4.1.0]heptane and Trifluoroacetic

Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61742.13.1.1.16 Method 16: Oxygenation of a Trialkylphosphine Selenide . . . . . . . . . . . . . . . . 617

42.13.2 Product Subclass 2: Trialkylphosphine Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . 618


42.13.2.1.1 Method 1: Addition of Dialkylphosphine Sulfides to Alkenes . . . . . . . . . . . . 61842.13.2.1.1.1 Variation 1: Base-Promote

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Volume42: OrganophosphorusCompounds (incl.RO—PandRN—P) · 2020. 11. 3. · 42.4.1.7.2 Variation 2: Reduction of Alkylphosphonates with Lithium Aluminum Hydride .....94 42.4.1.7.3