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Title: Stereochemical Control via Chirality Pairing: Stereodivergent Syntheses of Enantioenriched Homoallylic Alcohols
Abstract

We report herein the development of stereodivergent syntheses of enantioenriched homoallylic alcohols using chiral nonracemic α‐CH2Bpin‐substituted crotylboronate. Chiral phosphoric acid (S)‐A‐catalyzed asymmetric allyl addition with the reagent gaveZanti‐homoallylic alcohols with excellent enantioselectivities andZ‐selectivities. When the enantiomeric acid catalyst (R)‐Awas utilized, the stereoselectivity was completely reversed andEanti‐homoallylic alcohols were obtained with highE‐selectivities and excellent enantioselectivities. By pairing the chirality of the boron reagent with the catalyst, two complementary stereoisomers of chiral homoallylic alcohols can be obtained selectively from the same boron reagent. DFT computational studies were conducted to probe the origins of the observed stereoselectivity. These reactions generate highly enantioenriched homoallylic alcohol products that are valuable for rapid construction of polyketide structural frameworks.

 
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Award ID(s):
2042353 1764328
NSF-PAR ID:
10307071
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie International Edition
Volume:
60
Issue:
45
ISSN:
1433-7851
Page Range / eLocation ID:
p. 24096-24106
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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