A catalytic asymmetric Strecker-type reaction: Interesting reactivity difference between TMSCN and HCN

Angewandte Chemie - International Edition

Volumn 39, Issue 9, 2000, Pages 1650-1652

  Takamura, Masahiro ^a   Hamashima, Yoshitaka ^a   Usuda, Hiroyuki ^a   Kanai, Motomu ^a   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

Aminonitriles; Asymmetric catalysis; Catalysts; Cyanides; Lewis acids

Indexed keywords

ALDEHYDE; HYDROCINNAMIC ACID DERIVATIVE; IMINE; PHOSPHONIC ACID DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL MODIFICATION; CHEMICAL REACTION; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0034595353     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(20000502)39:9<1650::AID-ANIE1650>3.0.CO;2-P     Document Type: Article

References (21)

1. A. Strecker, Ann. Chem. Pharm. 1850, 75, 27-45.
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7. e) C. A. Krueger, K. W. Kuntz, C. D. Dzierba, W. G. Wirschun, J. D. Gleason, M. L. Snapper, A. H. Hoveyda, J. Am. Chem. Soc. 1999, 121, 4284-4285;
8. f) E. J. Corey, M. J. Grogan, Org. Lett. 1999, 1, 157-160.
9. The imines prepared from hydrocinnamaldehyde and n-nonanal reported in ref. [2d] had 83% ee (55% yield) and 74% ee (72% yield), respectively. The imine from n-heptanal in ref. [2f] was obtained with 63% ee. Recently, Kobayashi succeeded in greatly improving the catalytic asymmetric Strecker-type reaction using aliphatic imines (personal communication).
10. Y. Hamashima, D. Sawada, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 1999, 121, 2641-2642.
11. A similar effect of iPrOH on the reaction rate has been reported by Hoveyda et al. in ref. [2e].
12. [4] gave less satisfactory results.
13. 2.
14. For the conversion of products from aliphatic imines into α-amino acid derivatives, see the Supporting Information.
15. The relative configuration of 6a was determined by X-ray crystallographic analysis of the cyclic carbonate derived from 6a. See Supporting Information.
16. When PhOH was added in one portion, the reaction pathway seemed to be nearly the same as under the best reaction conditions. Thus, the ee values of the product 4a in these kinetic studies were 95% (in the absence of PhOH) and 88% (20 mol % of PhOH).
17. 1H NMR spectroscopic studies.
18. 3SnCN), HCN works as the reactive nucleophile.
19. [2e]
20. K. Mai, G. Patil, J. Org. Chem. 1986, 51, 3545-3548.
21. For the discussion about the role of the proton source in the catalytic asymmetric Strecker-type reaction, see ref.[2e].