Catalytic enantioselective conjugate addition of cyanide to α,β-unsaturated N-acylpyrroles

Journal of the American Chemical Society

Volumn 127, Issue 2, 2005, Pages 514-515

  Mita, Tsuyoshi ^a   Sasaki, Kazuki ^a   Kanai, Motomu ^a,b   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b JAPAN SCIENCE AND TECHNOLOGY AGENCY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

4 AMINO 3 PHENYLBUTYRIC ACID; 4 AMINOBUTYRIC ACID; BETA AMINO ACID; CARBOXYLIC ACID DERIVATIVE; CINNAMIC ACID DERIVATIVE; CYANIDE; CYCLOPENTANEDICARBOXYLIC ACID; GADOLINIUM; PREGABALIN; PYRROLE DERIVATIVE; UNCLASSIFIED DRUG;

ADDITION REACTION; ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHIRALITY; ENANTIOSELECTIVITY; STRECKER SYNTHESIS; SYNTHESIS;

CATALYSIS; CINNAMATES; CYANIDES; GADOLINIUM; GAMMA-AMINOBUTYRIC ACID; ORGANOMETALLIC COMPOUNDS; PYRROLES; STEREOISOMERISM;

EID: 12944296640     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja043424s     Document Type: Article

References (16)

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6. Kinetic studies and labeling experiments supported this reaction mechanism in the catalytic enantioselective cyanosilylation of ketones using the gadolinium complex: Yabu, K.; Masumoto, S.; Yamasaki, S.; Hamashima, Y.; Kanai, M.; Du, W.; Curran, D. P.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 9908.
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9. Catalysts prepared from other lanthanide alkoxides produced less satisfactory results.
10. 3 (0.2 M in THF, 75 μL, 0.015 mmol) was added to a solution of 2 (13.8 mg, 0.030 mmol) in THF (0.3 mL) at 0°C. The mixture was stirred at 45°C for 1 h, and then the solvent was evaporated at ambient temperature. After drying the resulting precatalyst under reduced pressure (<5 mmHg) for 1.5 h. substrate 7f (53.1 mg. 0.30 mmol) in propionitrile (500 μL) was added at room temperature, then cooled to -20°C. After 20 min, TMSCN (20 μL, 0.15 mmol) was added, and after 10 min, HCN (4 M in propionitrile stock solution, 150 μL, 0.60 mmol) was added to start the reaction.
11. The cyanide addition proceeded with high enantioselectivity. Lack of the diastereoselectivity is due to the nonstereoselective protonation of the intermediate enolate.
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14. Pregabalin has a (3S) configuration: (a) Silverman, R. B.; Andruszkiewicz, R.; Yuen, P.-W.; Sobieray, D. M.; Franklin, L. C.; Schwindt, M. A. U.S. Patent 5,563,175, 1996. For recent catalytic enantioselective synthesis of pregabalin, see: (b) Hoge, G. J. Am. Chem. Soc. 2003, 125, 10219, and ref 1a. For a practical synthesis of (ent)-ligand 2, see: (c) Kato, N.; Tomita, D.; Maki, K.; Kanai, M.; Shibasaki, M. J. Org. Chem. 2004, 69, 6128.
15. Pregabalin has a (3S) configuration: (a) Silverman, R. B.; Andruszkiewicz, R.; Yuen, P.-W.; Sobieray, D. M.; Franklin, L. C.; Schwindt, M. A. U.S. Patent 5,563,175, 1996. For recent catalytic enantioselective synthesis of pregabalin, see: (b) Hoge, G. J. Am. Chem. Soc. 2003, 125, 10219, and ref 1a. For a practical synthesis of (ent)-ligand 2, see: (c) Kato, N.; Tomita, D.; Maki, K.; Kanai, M.; Shibasaki, M. J. Org. Chem. 2004, 69, 6128.
16. Pregabalin has a (3S) configuration: (a) Silverman, R. B.; Andruszkiewicz, R.; Yuen, P.-W.; Sobieray, D. M.; Franklin, L. C.; Schwindt, M. A. U.S. Patent 5,563,175, 1996. For recent catalytic enantioselective synthesis of pregabalin, see: (b) Hoge, G. J. Am. Chem. Soc. 2003, 125, 10219, and ref 1a. For a practical synthesis of (ent)-ligand 2, see: (c) Kato, N.; Tomita, D.; Maki, K.; Kanai, M.; Shibasaki, M. J. Org. Chem. 2004, 69, 6128.