Toward a Unified Mechanism for Oxoammonium Salt-Mediated Oxidation Reactions: A Theoretical and Experimental Study Using a Hydride Transfer Model

被引：59

作者：

Hamlin, Trevor A. ^{[1
]}

Kelly, Christopher B. ^{[1
]}

Ovian, John M. ^{[1
]}

Wiles, Rebecca J. ^{[1
]}

Tilley, Leon J. ^{[2
]}

Leadbeater, Nicholas E. ^{[1
,3
]}

机构：

[1] Univ Connecticut, Dept Chem, Storrs, CT 06269 USA

[2] Stonehill Coll, Dept Chem, Easton, MA 02357 USA

[3] Univ Connecticut, Ctr Hlth, Dept Community Med & Hlth Care, Farmington, CT 06030 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2015年 / 80卷 / 16期

基金：

美国国家科学基金会;

关键词：

MOLECULAR-ORBITAL METHODS; GAUSSIAN-TYPE BASIS; AEROBIC OXIDATION; ALCOHOLS; TEMPO; TETRAFLUOROBORATE; CATALYST; ALKENES; ETHERS; ORGANOCATALYST;

D O I：

10.1021/acs.joc.5b01240

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A range of oxoammonium salt-based oxidation reactions have been explored computationally using density functional theory (DFT), and the results have been correlated with experimentally derived trends in reactivity. Mechanistically, most reactions involve a formal hydride transfer from an activated C-H bond to the oxygen atom of the oxoammonium cation. Several new potential modes of reactivity have been uncovered and validated experimentally.

引用

页码：8150 / 8167

页数：18

共 79 条

[1] Tropylium Ion Mediated α-Cyanation of Amines [J].