72524-23-3Relevant academic research and scientific papers
Stereoselective Acid-Catalyzed Claisen Rearrangements
Daub, William G.,Shanklin, Paula L.,Tata, Claudia
, p. 3402 - 3405 (1986)
An alkyl substituent in the 2-position of an E trisubstituted allylic alcohol confers significant diastereoselectivity on ortho ester and ketal Claisen rearrangements of the system.
Acyclic Stereoselection in the Ortho Ester Claisen Rearrangement
Daub, G. William,Edwards, James P.,Okada, Carol R.,Allen, Jana Westran,Maxey, Claudia Tata,Wells, Matthew S.,Goldstein, Alexandra S.,Dibley, Michael J.,Wang, Clarence J.,Ostercamp, Daniel P.,Chung, Steven,Cunningham, Paula Shanklin,Berliner, Martin A.
, p. 1976 - 1985 (2007/10/03)
The ortho ester Claisen rearrangement of trisubstituted allylic alcohols exhibits significant levels of diastereoselection. In E allylic alcohols, a 1,3-diaxial interaction develops in the chairlike transition state leading to the anti isomer, rendering the reaction syn selective by a factor of 3-5 to 1. In Z allylic alcohols, the 1,3-diaxial interaction develops in the transition state leading to the syn isomer, generating an anti:syn selectivity of 6-15 to 1. The relative stereochemistry of the syn isomer was confirmed independently by the synthesis of the mycotoxin botryodiplodin.
