Catalytic Effects of Ammonium and Sulfonium Salts and External Electric Fields on Aza-Diels-Alder Reactions

被引：20

作者：

He, Cyndi Qixin ^{[1
]}

Lam, Ching Ching ^{[2
]}

Yu, Peiyuan ^{[1
]}

Song, Zhihui ^{[3
]}

Chen, Maggie ^{[1
]}

Lam, Yu-hong ^{[1
]}

Chen, Shuming ^{[1
]}

Houk, K. N. ^{[1
]}

机构：

[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

[2] Imperial Coll London, Dept Chem, London SW7 2AZ, England

[3] Univ Maryland, Dept Chem & Biochem, College Pk, MD 20742 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2020年 / 85卷 / 04期

基金：

美国国家科学基金会;

关键词：

FUNCTIONAL-GROUP ARRAYS; HYDROGEN-BONDING CATALYSIS; TETRAALKYLAMMONIUM SALTS; ELECTROSTATIC CATALYSIS; SYNTHETIC RECEPTORS; ENERGIES; CHEMISTRY; STEREOSELECTIVITY; REGIOSELECTIVITY; CYCLOADDITION;

D O I：

10.1021/acs.joc.9b03446

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The mechanism of the aza-Diels-Alder reaction catalyzed by tetraalkylammonium or trialkylsulfonium salts is explored with density functional theory. Favorable electrostatic interactions between the dienophile and the charged catalyst stabilize the highly polar transition state, leading to lower free energy barriers and higher dipole moments. Endo selectivity is predicted for both uncatalyzed and catalyzed systems. We also computationally evaluate the effects of oriented external electric fields (EEFs) on the same aza-Diels-Alder reaction, demonstrating that very strong EEFs would be needed to achieve the catalytic strength of these cationic catalysts.

引用

页码：2618 / 2625

页数：8

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