Rh-catalyzed decarbonylation of conjugated ynones via carbon-alkyne bond activation: reaction scope and mechanistic exploration via DFT calculations

被引：68

作者：

Dermenci, Alpay ^{[1
]}

Whittaker, Rachel E. ^{[1
]}

Gao, Yang ^{[2
,3
]}

Cruz, Faben A. ^{[1
]}

Yu, Zhi-Xiang ^{[2
]}

Dong, Guangbin ^{[1
]}

机构：

[1] Univ Texas Austin, Dept Chem, Austin, TX 78712 USA

[2] Peking Univ, Coll Chem, Key Lab Bioorgan Chem & Mol Engn, BNLMS, Beijing 100871, Peoples R China

[3] Cent China Normal Univ, Coll Chem, Minist Educ, Key Lab Pesticide & Chem Biol, Wuhan 430079, Hubei, Peoples R China

来源：

CHEMICAL SCIENCE | 2015年 / 6卷 / 05期

关键词：

EFFECTIVE CORE POTENTIALS; C-CN ACTIVATION; INTRAMOLECULAR CYANOAMIDATION; 3,3-DISUBSTITUTED OXINDOLES; MOLECULAR CALCULATIONS; COMPLEX-FORMATION; BITE ANGLE; CLEAVAGE; OLEFINS; CARBOCYANATION;

D O I：

10.1039/c5sc00584a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In this full article, detailed development of a catalytic decarbonylation of conjugated monoynones to synthesize disubstituted alkynes is described. The reaction scope and limitation has been thoroughly investigated, and a broad range of functional groups including heterocycles were compatible under the catalytic conditions. Mechanistic exploration via DFT calculations has also been executed. Through the computational study, a proposed catalytic mechanism has been carefully evaluated. These efforts are expected to serve as an important exploratory study for developing catalytic alkyne-transfer reactions via carbon-alkyne bond activation.

引用

页码：3201 / 3210

页数：10