Manganese-Catalyzed Oxidative Azidation of C(sp(3))-H Bonds under Electrophotocatalytic Conditions

作者:Niu, LB (Niu, Linbin)[ 1 ] ; Jiang, CY (Jiang, Chongyu)[ 1 ] ; Liang, YW (Liang, Yuwei)[ 1 ] ; Liu, DD (Liu, Dingdong)[ 1 ] ; Bu, FX (Bu, Faxiang)[ 1 ] ; Shi, RY (Shi, Renyi)[ 1 ] ; Chen, H (Chen, Hong)[ 1 ] ; Chowdhury, AD (Chowdhury, Abhishek Dutta)[ 1 ] ; Lei, AW (Lei, Aiwen)[ 1,2 ]

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

卷: 142 期: 41 页: 17693-17702

DOI: 10.1021/jacs.0c08437

出版年: OCT 14 2020

文献类型:Article

摘要

The selective installation of azide groups into C(sp(3))-H bonds is a priority research topic in organic synthesis, particularly in pharmaceutical discovery and late-stage diversification. Herein, we demonstrate a generalized manganese-catalyzed oxidative azidation methodology of C(sp(3))-H bonds using nucleophilic NaN3 as an azide source under electrophotocatalytic conditions. This approach allows us to perform the reaction without the necessity of adding an excess of the substrate and successfully avoiding the use of stoichiometric chemical oxidants such as iodine(III) reagent or NFSI. A series of tertiary and secondary benzylic C(sp(3))-H, aliphatic C(sp(3))-H, and drug-molecule-based C(sp(3))-H bonds in substrates are well tolerated under our protocol. The simultaneous gram-scale synthesis and the ease of transformation of azide to amine collectively advocate for the potential application in the preparative synthesis. Good reactivity of the tertiary benzylic C(sp(3))-H bond and selectivity of the tertiary aliphatic C(sp(3))-H bond in substrates to incorporate nitrogen-based functionality at the tertiary alkyl group also provide opportunities to manipulate numerous potential medicinal candidates. We anticipate our synthetic protocol, consisting of metal catalysis, electrochemistry, and photochemistry, would provide a new sustainable option to execute challenging organic synthetic transformations.

关键词

KeyWords Plus:C-H FUNCTIONALIZATION; BETA-KETO-ESTERS; CLICK CHEMISTRY; METAL-FREE; AMINATION; ELECTROCHEMISTRY; ALKANES; AZIDONATION; EFFICIENT; REAGENT

作者信息

通讯作者地址:

Wuhan University Wuhan Univ, Inst Adv Studies IAS, Coll Chem & Mol Sci, Wuhan 430072, Peoples R China.

Chinese Academy of Sciences Shanghai Institute of Organic Chemistry, CAS Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China.

通讯作者地址: Lei, AW (通讯作者)

Wuhan Univ, Inst Adv Studies IAS, Coll Chem & Mol Sci, Wuhan 430072, Peoples R China.

通讯作者地址: Lei, AW (通讯作者)

Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China.

地址:

[ 1 ]‎ Wuhan Univ, Inst Adv Studies IAS, Coll Chem & Mol Sci, Wuhan 430072, Peoples R China

[ 2 ]‎ Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China

电子邮件地址:aiwenlei@whu.edu.cn