Hydrogen-Bond-Enabled Dynamic Kinetic Resolution of Axially Chiral Amides Mediated by a Chiral Counterion

被引：48

作者：

Fugard, Alison J. ^{[1
]}

Lahdenpera, Antti S. K. ^{[1
]}

Tan, Jaqueline S. J. ^{[1
]}

Mekareeya, Aroonroj ^{[1
]}

Paton, Robert S. ^{[2
]}

Smith, Martin D. ^{[1
]}

机构：

[1] Univ Oxford, Chem Res Lab, 12 Mansfield Rd, Oxford OX1 3TA, England

[2] Colorado State Univ, Dept Chem, Ft Collins, CO 80523 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 09期

基金：

英国工程与自然科学研究理事会;

关键词：

axial chirality; counterion; energy transfer; phase transfer; visible light; NON-BIARYL ATROPISOMERS; ENANTIOSELECTIVE SYNTHESIS; RACEMIZATION; SILYLATION; ROTATION; LIGANDS;

D O I：

10.1002/anie.201814362

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Non-biaryl atropisomers are valuable in medicine, materials, and catalysis, but their enantioselective synthesis remains a challenge. Herein, a counterion-mediated O-alkylation method for the generation of atropisomeric amides with an er up to 99:1 is outlined. This dynamic kinetic resolution is enabled by the observation that the rate of racemization of atropisomeric naphthamides is significantly increased by the presence of an intramolecular O-H center dot center dot center dot NCO hydrogen bond. Upon O-alkylation of the H-bond donor, the barrier to rotation is significantly increased. Quantum calculations demonstrate that the intramolecular H-bond reduces the rotational barrier about the aryl-amide bond, stabilizing the planar transition state for racemization by approximately 40 kJ mol(-1), thereby facilitating the observed dynamic kinetic resolution.

引用

页码：2795 / 2798

页数：4

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