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Literature PresentationZhenjie Lu
Jan 12, 2006
1. Seayad, J.; Seayad, A. M.; List, B. J. Am. Chem. Soc. 2006, ASAP.2. Storer, R. L.; Carrera, D. E.; Ni, Y.; MacMillan, D. W. C. J. Am. Chem. Soc. 2006,128, 84.3. Hoffmann, S.; Seayad, A. M.; List, B. Angew. Chem. Int. Ed. 2005, 44, 7424.4. Rowland, G. B.; Zhang, H.; Rowland, E. B.; Chennamadhavuni, S.; Wang, Y.; Antilla, J. C. J. Am.
Chem. Soc. 2005,127, 15696.5. Uraguchi, D.; Sorimachi, K.; Terada, M. J. Am. Chem. Soc. 2005,127, 9360.6. Uraguchi, D.; Sorimachi, K.; Terada, M. J. Am. Chem. Soc. 2005,127, 11804.7. Uraguchi, D.; Terada, M. J. Am. Chem. Soc. 2004,126, 5356.8. Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Angew. Chem. Int. Ed. 2004, 43, 1566.9. Akiyama, T.; Morita, H.; Itoh, J.; Fuchibe, K. Org. Lett. 2005, 7, 2583.
Recent applications of chiral binaphthol-derived phosphoric acid in catalytic
asymmetric reactions
R
O
O
R
PO
OH
Introduction
‘Stereoselective chemical transformations perhaps have over emphasized the virtue ofmetal catalysis but this picture is changing rapidly; fast developing metal-free catalysiswith small organic molecules as been described as utilizing “artificial enzymes” or being“enzyme mimetics”.’
Schreiner, P. R. Chem. Soc. Rev. 2003, 32, 289.
advantages of using Bronsted acida. Metal-free chiral organocatalysts exhibit catalytic activity by themselves.b. Organocatalysts are generally stable in air and easily stored.c. Chiral Bronsted acid catalysts would electrophilically activate C=O or C=N
bond, and cause chiral induction.
Chiral Binaphthol-Derived Phosphoric Acid
The tetradentate structure around the phosphorus(V) prevent free rotation at thephosphorus center by formation of a ring structure. This cannot be found in othercarboxylic and sulfonic Bronsted acids.
R
O
O
R
PO
OH
The appropriate acidity (pKa of diethylphosphate is 1.39) should catch up thesubstrate through hydrogen bonding without loose ion-pair formation.
The phosphoryl oxygen should function as a Lewis basic site, and thus aphosphoric acid could function as a bifunctional catalyst.
Schreiner, P. R. Chem. Soc. Rev. 2003, 32, 289.
Plausible hydrophosphonylation mechanism
I. Bronsted Acid Catalyzed Mannich - type Reaction
Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Angew. Chem. Int. Ed. 2004, 43, 1566.
Bulky Bronsted acid and aromatic solvent gave better selectivity.
I. Bronsted Acid Catalyzed Mannich - type Reaction
Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Angew. Chem. Int. Ed. 2004, 43, 1566.
Akiyama’s catalyst and results.O
OP
O
OH
NO2
NO2
Akiyama's catalyst
I. Bronsted Acid Catalyzed Mannich - type Reaction
Uraguchi, D.; Terada, M. J. Am. Chem. Soc. 2004,126, 5356.
Terada’s catalyst and results.
O
OP
O
OH
Terada's catalyst in Mannich reaction
Uraguchi, D.; Sorimachi, K.; Terada, M. J. Am. Chem. Soc. 2005,127, 11804.
II. Bronsted Acid Catalyzed Friedel Crafts - type Reactions
Halogenated solvent gave better results than ethereal or aromatic solvents. (87% yield, 97%ee vs. 70% yield, 83% ee in THF or 88% yield, 83% ee in toluene.)
a. 0.1 M in (CH2Cl)2 at -35 oC for 24h.
II. Bronsted Acid - Catalyzed Friedel Crafts - type Reactions
II. Bronsted Acid - Catalyzed Friedel Crafts - type Reactions
Uraguchi, D.; Sorimachi, K.; Terada, M. J. Am. Chem. Soc. 2005,127, 9360.
3 mol% of 5toluene, rt, 24h
II. Bronsted Acid Catalyzed Friedel Crafts - type Reactions:Pictet-Spengler Reaction
1) Taylor, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 10558.2) Seayad, J.; Seayad, A. M.; List, B. J. Am. Chem. Soc. 2006, ASAP.
Pictet-Spengler Reaction:
Jacobsen’s approach
List’s approach
N R
R'
R''O X chiral thiourea catalyst -HX
R2
R3
NH2
R1
! "+
R4 R5
Oprotic orlewis acid
R2
R3
NR1
! "
R4
R5
R2
R3
NHR1
! "
R4 R5
tetrahydroisoquinoline
II. Bronsted Acid Catalyzed Friedel Crafts - type Reactions:Pictet-Spengler Reaction
Seayad, J.; Seayad, A. M.; List, B. J. Am. Chem. Soc. 2006, ASAP.
O
OP
O
OH
i-Pr i-Pr
i-Pr
i-Pri-Pr
i-Pr
5 List's catalyst
This reaction toleratesaromatic aldehydes (at-10oC in CH2Cl2) (entry12-16).
III. Bronsted Acid Catalyzed Reductive Amination
Rueping, M.; Sugiono, E.; Azap, C.; Theissmann, T.; Bolte, M. Org. Lett. 2005, 7, 3781.
O
O
PO
OH
CF3
CF3
CF3
CF3
Proposed mechanism
(HEH)
Rueping’s approach:
Catalytic asymmetrichydrogenation to imine is limited.
III. Bronsted Acid Catalyzed Reductive Amination
1) Rueping, M.; Sugiono, E.; Azap, C.; Theissmann, T.; Bolte, M. Org. Lett. 2005, 7, 3781.2) Hoffmann, S.; Seayad, A. M.; List, B. Angew. Chem. Int. Ed. 2005, 44, 7424. 3) Storer, R. L.; Carrera, D. E.; Ni, Y.; MacMillan, D. W . C. J. Am. Chem. Soc. 2006,128, 84.
Rueping’s approach:
R = Ar, 46-91% yield, 70-82% ee.
List’s approach:
R = Ar, i-Pr, 80-98% yield, 80-93% ee.One example that from ketone to a deprotected amine (R = Ph, 75% overall yield, 88% ee).
R
O
O
R
PO
OH
Rueping's A1: R = 3,5-(CF3)-phenylList's A2: R = 2,4,6-(i-Pr)-phenylMacMillan's A3: R = SiPh3
A
R CH3
NPMP HEH, 20mol% A1
benzene, 60oC
R CH3
HNPMP
R CH3
NPMP HEH, 1 mol% A2
toluene, 35oC
R CH3
HNPMP
MacMillan’s approach:
R = Ar, R’= OMe, 60-87% yield, 83-95% ee.R = alkyl, R’= OMe, 49-75% yield, 81-94% ee.R = Ar, R’= aryl, 55-92% yield, 91-95% ee.
R CH3
O
+
NH2
R'HEH, 10 mol% A3
5 A MS, 40-50oC
benzene, 24-96h
R CH3
HN
R'
IV. Bronsted Acid Catalyzed Hydrophosphonylation
Akiyama, T.; Morita, H.; Itoh, J.; Fuchibe, K. Org. Lett. 2005, 7, 2583.
V. Bronsted Acid Catalyzed Imine Amidation
Rowland, G. B.; Zhang, H.; Rowland, E. B.; Chennamadhavuni, S.; W ang, Y.; Antilla, J. C. J. Am. Chem. Soc.2005,127, 15696.
catalyst A: 91-99% yield, catalyst B: 91-99% yield.
Bronsted Acid - Catalyzed Imine Amidation
Rowland, G. B.; Zhang, H.; Rowland, E. B.; Chennamadhavuni, S.; W ang, Y.; Antilla, J. C. J. Am. Chem. Soc.2005,127, 15696.
Toluene was used assolvent in entry 8-13.
Conclusion
Ph
Ph
O
OP
O
OH
Antilla -imine amidation
O
OP
O
OH
Terada - Mannich
O
OP
O
OH
NO2
NO2Akiyama - Mannich
O
OP
O
OH
Terada - aza-Friedel-Crafts
anth
O
O
anth
PO
OH
Terada - alkylation of diazoester
O
OP
O
OH
i-Pr i-Pr
i-Pr
i-Pri-Pr
i-Pr
List - Pictet-Spengler and amination
O
OP
O
OH
CF3
CF3
CF3
CF3
Rueping - amination andAkiyama - hydrophosphonylation
Si
O
O
Si
PO
OH
Ph Ph
Ph
PhPhMacMillan - amination
PhR
O
O
R
PO
OH
Bronsted Acid - Catalyzed Mannich-type Reaction-Deastereoselectivity
Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Angew. Chem. Int. Ed. 2004, 43, 1566.
O
OP
O
OH
NO2
NO2
Akiyama's catalyst
Bronsted Acid - Catalyzed Friedel Crafts - type ReactionsPictet-Spengler Reaction
1) Taylor, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 10558.2) Seayad, J.; Seayad, A. M.; List, B. J. Am. Chem. Soc. 2006, ASAP.
Jacobsen’s approach
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