RhII-Catalyzed β-C(sp2)-H Alkylation of Enol Ethers, Enamides and Enecarbamates with α-Diazo Dicarbonyl Compounds

被引：9
|
作者：
McLarney, Brett D. [1 ]
Cavitt, Marchello A. [1 ]
Donnell, Theodore M. [1 ]
Musaev, Djamaladdin G. [3 ]
France, Stefan [1 ,2 ]
机构：
[1] Georgia Inst Technol, Sch Chem & Biochem, Atlanta, GA 30332 USA
[2] Georgia Inst Technol, Petit Inst Bioengn & Biosci, Atlanta, GA 30332 USA
[3] Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30332 USA
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2017年 / 23卷 / 05期
基金：
美国国家科学基金会;
关键词：
addition/elimination; alkylation; C-H activation; diazo compounds; rhodium; EFFECTIVE CORE POTENTIALS; DIMETHYL DIAZOMALONATE; MOLECULAR CALCULATIONS; REACTION COORDINATE; ENAMINES; FUNCTIONALIZATION; ARYLDIAZOACETATES; DIHYDROFURANS; REARRANGEMENT; HYBRIDIZATION;
D O I：
10.1002/chem.201604518
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A Rh-II-catalyzed method for intermolecular alkylation of the beta-C(sp(2))-H bond of enol ethers, enamides, and enecarbamates with alpha-diazo-1,3-dicarbonyl compounds is reported. The products are formed in up to 99% yield and can be readily derivatized under a variety of conditions. By utilizing a combination of experimental and computational studies, the presumptive addition-elimination reaction mechanism was investigated and found to proceed under thermodynamic control at higher temperature. The acquired fundamental knowledge was translated into a strategic reaction design and yielded the first example of the beta-C-H functionalizations of acyclic enol ethers using a-diazo-1,3-dicarbonyl compounds.
引用
收藏
页码：1129 / 1135
页数：7
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