Rhodium-Catalyzed Cyclocarbonylation of Ketimines via C-H Bond Activation

被引：52

作者：

Gao, Bao ^{[1
,2
]}

Liu, Song ^{[1
,3
]}

Lan, Yu ^{[3
]}

Huang, Hanmin ^{[1
]}

机构：

[1] Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China

[2] Univ Chinese Acad Sci, Beijing 100049, Peoples R China

[3] Chongqing Univ, Sch Chem & Chem Engn, Chongqing 400030, Peoples R China

来源：

ORGANOMETALLICS | 2016年 / 35卷 / 10期

基金：

中国国家自然科学基金;

关键词：

ONE-POT SYNTHESIS; OXIDATIVE CARBONYLATION; C(SP(3))-H BONDS; REGIOSELECTIVE CARBONYLATION; STEREOSELECTIVE-SYNTHESIS; EFFICIENT SYNTHESIS; 3+2 CYCLOADDITION; ALIPHATIC-AMINES; MOLECULAR-OXYGEN; TERMINAL ALKYNES;

D O I：

10.1021/acs.organomet.6b00072

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A novel rhodium-catalyzed oxidative cyclocarbonylation of ketimines via cleavage of two C-H bonds was established, which provided a direct and reliable method for the synthesis of a wide range of 3-methyleneisoindolin-1-ones with mostly moderate yields. Preliminary experimental mechanistic studies and DFT calculations revealed that this reaction proceeds via imine-enamine tautomerization, N-H cleavage, C-H bond activation, CO insertion, and reductive elimination. The mechanism studies further ruled out an isolated cyclometalated rhodium complex being involved in the present reaction, which was different from many other documented rhodium-catalyzed C-H cyclization reactions.

引用

页码：1480 / 1487

页数：8

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