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Catalytic enantioselective construction of beta-quaternary carbons via a conjugate addition of cyanide to beta,beta-disubstituted alpha,beta-unsaturated carbonyl compounds.

Authors
  • Tanaka, Yuta
  • Kanai, Motomu
  • Shibasaki, Masakatsu
Type
Published Article
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Publication Date
Jul 07, 2010
Volume
132
Issue
26
Pages
8862–8863
Identifiers
DOI: 10.1021/ja1035286
PMID: 20536134
Source
Medline
License
Unknown

Abstract

The first general catalytic enantioselective conjugate addition of cyanide to beta,beta-disubstituted alpha,beta-unsaturated ketones and N-acylpyrroles was developed using a strontium catalyst derived from Sr(O(i)Pr)(2) and new chiral ligand 5. The reaction exhibited excellent enantioselectivity and a wide substrate scope using 0.5-10 mol % catalyst. 1,4-Adducts containing beta-quaternary carbons were exclusively produced over 1,2-adducts. ESI-MS analysis of the strontium catalyst indicated that the active catalyst was a trimetallic Sr/5 = 3:5 complex. The exclusive 1,4-selectivity was partly due to the ability of the strontium complex to promote both a retro-cyanation reaction from the 1,2-adducts and highly enantioselective conjugate cyanation.

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