Imprimatur:

Date, Signaturetc0620ss.fm 2/20/20

Reviews and Full Papers in Chemical Synthesis

2020Vol. 52, No. 6

March IISyn thesis

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Synthesis 2020, 52, 781–795DOI: 10.1055/s-0039-1690044

A. N. Reznikov*Y. N. KlimochkinSamara State Technical University, Russian Federation

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Recent Developments in Highly Stereoselective Michael Addition Reactions Catalyzed by Metal Complexes

FG

R

R'EWG

R'

O

NCOOR'

R

N

R'

O

R''

OH

R'

R'

R

O

R

functionalized ketonesindolin-2-ones

nitroolefinsenones

unsaturatedimines

unsaturatedesters

O

Michael donors Michael acceptors

R'

t-But-Bu

para-quinonemethidesaldimino esters and their

cyclic analogues

Metal complexcatalysis

enantioselectivity +diastereoselectivity

naphthols

alkynones

Review

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Synthesis 2020, 52, 796–806DOI: 10.1055/s-0039-1690789

S.-Z. SongY. Dong*G.-P. Ge*Q. LiW.-T. Wei*Ningbo University, P. R. of China

Recent Advances in Radical Nitration Using tert-Butyl Nitrite S

hort Review

796

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Synthesis 2020, 52, 807–818DOI: 10.1055/s-0039-1690046

S. W. Youn*Hanyang University, Republic of Korea

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Transition-Metal-Catalyzed Annulative Coupling Cascade for the Synthesis of 3-Methyleneisoindolin-1-ones

N

O

RR'

C–C & C–CC–C & C–NC–C & C–N

R1

R2

C–N & C–C

C–C, C–C, C–N, & C–NC–C, C–N, & C–N

Transition-Metal-Catalyzed Annulative Coupling Cascades

[Pd]

[Rh]

[Ru]

[Cu]

[Co]

[Ni]

Formation of Multiple C–C/C–N Bonds

C–C & C–N

S

hort Review

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Synthesis 2020, 52, 819–833DOI: 10.1055/s-0039-1691561

J.-C. Hsieh*H.-L. SuTamkang University, Taiwan

as

Synthesis of N-Heterocycles via Transition-Metal-Catalyzed Tandem Addition/Cyclization of a Nitrile

R C N

R C N [M]

[M] = MR'C N

R

R' M

Nu–C N

Nu

R LA[M] = LA

1,2-insertion

nucleophilic addition

R' C N

R'

R

radical addition (iminyl radical)

s-coordination

[M]

further cyclization for the formation of N-heterocycles

N N

NR

NH

R

N

N

R

N

N

R

HR'

NH

NN

NR

R'

R"

NR R'

N

N

–

S

hort Review

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Synthesis 2020, 52, 834–846DOI: 10.1055/s-0039-1690801

Q. GaoZ.-S. LiuY. HuaS. ZhouH.-G. Cheng*Q. Zhou*Wuhan University, P. R. of China

Alkyl Tosylates as Alkylating Reagents in the Catellani Reaction

Pd/NBEcooperative catalysis

+ R3

IR1 R1

R3

R2

+

CN(±)

45 examplesup to 97% yield

NBE-CN as the catalytic mediator broad substrate scopeeasily accessible starting materials

[NBE](20 mol%)

scalable protocol

R2 OTs

Feature

834

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Synthesis 2020, 52, 847–852DOI: 10.1055/s-0039-1690730

B. MorraN. A. MorraD. G. MacDonaldB. L. Pagenkopf*The University of Western Ontario, Canada

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Gram-Scale Synthesis of the Co(nmp)2 Catalyst to Prepare trans-2,5-Disubstituted Tetrahydrofurans by the Aerobic Oxidative Cyclization of Pent-4-en-1-ols

iPrOH, 1 atm air55 °C, 16 h

Co(nmp)2 (10 mol%)tBuOOH (10 mol%)

BnO

OH OOH

HH

BnO

single diastereomer93% yield

PSP

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Synthesis 2020, 52, 853–860DOI: 10.1055/s-0039-1690763

M. KohlhaasF. LutzN. ParansothyF. Octa-SmolinC. WölperJ. Niemeyer*University of Duisburg-Essen, Germany

as

Synthesis of Bis-BINOL Derivatives: Linking via the 3-, 4-, or 5-Position by Generation of Suitable C1-Symmetric Precursors

OH

OH

HO

HO

LINKER3

3

OH

OH

OH

OH

4

LINK

ER

4

OH

OH

OH

OH

5

LINK

ER

5

Paper

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Synthesis 2020, 52, 861–872DOI: 10.1055/s-0039-1690760

M.-Y. Chang*K.-T. ChenY.-L. TsaiH.-Y. ChenKaohsiung Medical University, TaiwanKaohsiung Medical University Hospital, Taiwan

One-Pot Access to 2-Aryl-3-(arylmethyl)chromones

NaOH (2 equiv)

MeOH (30 mL)50 °C, 10 h

2

3

O

OH

O

O

Ar ArAr'

Ar'

O

Ar'+ 2 + 2 H2Oeasy-operational

27–86% yields

>36 examples

Ar = Ph, 4-FC6H3, 4-ClC6H3, 4-BrC6H3, 1-naphthyl, 5-MeOC6H3, 4-MeOC6H3, 3-MeOC6H3, 5-BuOC6H3, 4-BuOC6H3, 3-BuOC6H3, 5-BnOC6H3, 4-BnOC6H3, 3-BnOC6H3, 4,6-Cl2C6H2, 4,6-F2C6H2, 4-MeC6H3, 2-naphthyl, 4-PhC6H3, 4-(4-FC6H4)C6H3, 4-(4-MeOC6H4)C6H3, 4-(2-naphthyl)C6H3, 4-(4-PhC6H4)C6H3 Ar' = pyridyl, phenyl, naphthyl, furyl, thienyl, benzofuryl, benzothienyl, quinolinyl

45

6

23

4

5

3

Paper

861

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Synthesis 2020, 52, 873–881DOI: 10.1055/s-0039-1690766

J. SkotnitzkiA. KremsmairB. KicinR. SaebV. RufP. Knochel*Ludwig-Maximilians-Universität, Germany

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Stereoselective anti-SN2′-Substitutions of Secondary Alkylcopper-Zinc Reagents with Allylic Epoxides: Total Synthesis of (3S,6R,7S)-Zingiberenol

R1 I

MeR1

Me

R2OHR1 Cu

Me

SN2'-substitution–10 °C, 12 h

ZnCl2

stable in THF

+1. tBuLi (inv. add.) –100 °C, 10 s

2. CuBr·P(OEt)3

–100 °C, 1 min

Me

Me (S)(S) (R)(R)

Me

(S)(S)OH

Me

(3S,6R,7S)-zingiberenol

9.7% yield over 8 steps; dr(C3,C6) = 99:1; dr(C6,C7) = 81:19

36

7 H

R4 H

HR2

R3

anti

H R4

O

R3

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Synthesis 2020, 52, 882–892DOI: 10.1055/s-0039-1691487

L. PruschinskiA.-L. LückeT. FreeseS.-R. KahnertS. MummelA. Schmidt*Clausthal University of Technolo-gy, Germany

as

Suzuki–Miyaura Cross-Couplings under Acidic Conditions

NO2

Cl

O2N NO2O2NPd(PPh3)4, 1,4-dioxane,

H2O, Na2CO3

pH 5.7O

98%

LiPhN

N OO

OO

O CH3COOH

B(OH)2

Paper

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Synthesis 2020, 52, 893–900DOI: 10.1055/s-0039-1690765

H.-L. LuF.-H. GuoT.-L. WangX.-C. WangZ.-J. Quan*Northwest Normal University, P. R. of ChinaGansu International Scientific and Technological CooperationBase of Water-Retention Chemi-cal Functional Materials, P. R. of China

Palladium-Catalyzed/Copper-Mediated Desulfurization and Arylation of Quinoline-2-(1H)-thione for Rapid Access to Quinoline Derivatives

HN

S

N

RR1B(OH)2 Pd(OAc)2, CuTC

DPEphos, 1,4-dioxane100 °C, 6 h

+

R1 R2R2R1

R2

or

H

R = aryl, alkyne

C–C bonds formation without an inert atmosphere 29 examples, up to 85% yield base-free

Paper

893

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Synthesis 2020, 52, 901–908DOI: 10.1055/s-0037-1610742

Y. LiuC. ZhangX. LiangX. ZengR. LuZ. FangS. WangY. LiuJ. Hu*Weifang Medical University, P. R. of China

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Synthesis of 2-Imidazolines via Palladium-Catalyzed Cyclization Reaction of 2,3-Allenyl Amines and Aryl Iodides

+

* Low toxicity * form C–C and C–N * Readily available substrates

R1INTs

R2 NH

N

R2 N

Ts R1Pd(PPh3)4

K2CO3/THF

19 examples: 48–78%

Paper

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Synthesis 2020, 52, 909–916DOI: 10.1055/s-0039-1691531

K. DziubaM. LubańskaK. M. Pietrusiewicz*Maria Curie-Skłodowska Univer-sity, Poland

as

Enantiodivergent Synthesis of Both PAMPO Enantiomers Using L-Menthyl Chloroacetate and Stereomutation at P in Classical Quaternisation Reactions

OP

OMeO O

P

OMeO

(SP)-PAMPO

P

O

(RP)-PAMPO

SP

OMeMe

P

O

OMeR

89%88%

89%

R = allyl R = 1E-propenyl

*

*

*

*

P Me

OMeO* CO2H

SP

RP

chromatography-free, multigram scale

96%

Paper

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Synthesis 2020, 52, 917–927DOI: 10.1055/s-0039-1690759

J. BanM. LimS. ShabbirJ. BaekH. Rhee*Hanyang University, Republic of Korea

Site-Specific Synthesis of Carbazole Derivatives through Aryl Homocoupling and Amination

NH2

Br

RNH

Br

R

O NH

R

O

HN

O

R NH

R R

R: CH3, F, Cl, i-Pr, t-Bu, CF3, OCH3, OCF3

Copper(0) powderUllmann homocouplingN-Acetylation

H3PO4

Intramolecular amination

Paper

917

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Synthesis 2020, 52, 928–932DOI: 10.1055/s-0039-1690809

Y. LiH. Guo*R. Fan*Fudan University, P. R. of China

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Iodobenzene-Catalyzed Oxidative Cyclization for the Synthesis of Highly Functionalized Cyclopropanes

R1

RO2C CO2RCO2RRO2C

EWGR1 EWG

EWG = NO2, COAr22 examplesgood yields

high diastereoselectivities

H

H

Ph IO–

I

+NBu4

PhI

ArCOOOHBu4NI ArCOOH

iodobenzene-catalyzed oxidative cyclization

Paper

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Synthesis 2020, 52, 933–941DOI: 10.1055/s-0039-1690039

R. BartolottaC. La Rosa*D. NavaUniversità degli Studi di Milano, Italy

as

New Strategy of Synthesis of Peramivir Analogues as Potential Neuraminidase Inhibitors

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Synthesis 2020, 52, 942–948DOI: 10.1055/s-0039-1691522

K. OhsawaH. ZhaoT. TokunagaC. ThomasA. GanesanY. MasudaT. Doi*Tohoku University, Japan

Stereoselective Synthesis of Protected L-allo-Enduracididine and L-Enduracididine via Asymmetric Nitroaldol Reaction

BocHN OtBu

O

O

BocHN OtBu

O

92%, dr 96:4

BocHN OtBu

O

asymmetricnitroaldol reaction

commonintermediate

L-allo-enduracididine(61%, 4 steps)

BocHN OtBu

OHN

NCbzCbzN

L-enduracididine(71%, 4 steps)

BocHN OtBu

OHN

NCbzCbzN

HO

O2N

HO

O2N

91%, dr 96:4

high diastereoselectivitymulti-gram scale synthesis

Paper

942