Model for the Enantioselectivity of Asymmetric Intramolecular Alkylations by Bis-Quaternized Cinchona Alkaloid-Derived Catalysts

A model for the stereoselectivity of intramolecular alkylations by N,N′-disubstituted cinchona alkaloids reported by Xiang et al. was established using density functional theory (DFT) calculations. The stereocontrol is based on the minimal distortion of the transition state (TS) and catalyst require...

Full description

Saved in:
Bibliographic Details
Published in:Journal of organic chemistry 2017-08, Vol.82 (16), p.8645-8650
Main Authors: He, Cyndi Qixin, Simon, Adam, Lam, Yu-hong, Brunskill, Andrew P. J, Yasuda, Nobuyoshi, Tan, Jiajing, Hyde, Alan M, Sherer, Edward C, Houk, K. N
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:A model for the stereoselectivity of intramolecular alkylations by N,N′-disubstituted cinchona alkaloids reported by Xiang et al. was established using density functional theory (DFT) calculations. The stereocontrol is based on the minimal distortion of the transition state (TS) and catalyst required to achieve favorable electrostatic interactions in the favored TS. Counterions must be included in computational modeling of ion-paired catalysis in order to reproduce experimental enantioselectivity.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.7b01577