Oxidative Alkane C-H Alkoxycarbonylation.
Directly utilizing a chemical feedstock to construct valuable compounds is an attractive prospect in organic synthesis. In particular, the combination of C(sp(3) )-H activation and oxidative carbonylation involving alkanes and CO gas is a promising and efficient method to synthesize carbonyl derivatives. However, due to the high C-H bond dissociation energy and low polarity of unactivated alkanes, the carbonylation of unactivated C(sp(3) )-H bonds still remains a great challenge. In this work, we introduce a palladium-catalyzed radical oxidative alkoxycarbonylation of alkanes to prepare numerous alkyl carboxylates. Various alkanes and alcohols were compatible, generating the desired products in up to 94 % yield. Remarkably, ethane, a constituent of natural gas, could be employed as a substrate under the standard reaction conditions. Preliminary mechanistic studies revealed a probable palladium-catalyzed radical process.
College of Chemistry and Molecular Sciences, The Institute for Advanced Studies, Wuhan University, Wuhan, 430072, P. R. China.
Lijun
L
Lu
College of Chemistry and Molecular Sciences, The Institute for Advanced Studies, Wuhan University, Wuhan, 430072, P. R. China.
Renyi
R
Shi
College of Chemistry and Molecular Sciences, The Institute for Advanced Studies, Wuhan University, Wuhan, 430072, P. R. China.
Luyao
L
Liu
College of Chemistry and Molecular Sciences, The Institute for Advanced Studies, Wuhan University, Wuhan, 430072, P. R. China.
Jingwen
J
Yan
National Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang, 330022, P. R. China.
Fangling
F
Lu
College of Chemistry and Molecular Sciences, The Institute for Advanced Studies, Wuhan University, Wuhan, 430072, P. R. China. aiwenlei@whu.edu.cn.|National Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang, 330022, P. R. China. aiwenlei@whu.edu.cn.
Aiwen
http://orcid.org/0000-0001-8417-3061
A
Lei
C−H activation; alkanes; carbonylation; palladium; radical reactions