Asymmetric induction in a [2,3] sigmatropic rearrangement. Biogenetic model

1973 ◽  
Vol 38 (19) ◽  
pp. 3438-3439 ◽  
Author(s):  
Barry M. Trost ◽  
William G. Biddlecom
Keyword(s):  
Sigmatropic Rearrangement ◽  
Asymmetric Induction

Asymmetric induction in the additions of anions of allylic sulfoxides to benzaldehyde

1980 ◽  
Vol 33 (12) ◽  
pp. 2635 ◽  
Author(s):  
DJ Antonjuk ◽  
DD Ridley ◽  
MA Smal
Keyword(s):  
Double Bond ◽  
Sigmatropic Rearrangement ◽  
Asymmetric Induction ◽  
Addition Reactions

Addition reactions of anions of aryl allyl sulfoxides to benzaldehyde proceed readily in moderate yields and afford mixtures of products resulting from α- and γ-attack on the allyl anion. The γ-products all possess the (E)-configuration around the double bond, and asymmetric induction occurs in the addition to the extent that the major/minor diastereomer ratio exceeds 2 : 1, generally. Electronic factors are believed to be responsible for this 'remote' asymmetric induction. Mixtures of all four possible diastereomers are observed in the products from α-attack and evidence is presented which suggests that the ratios of these products are as a result of epimerization of two of the chiral centres by [2,3] sigmatropic rearrangement.

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