Directed C-H Functionalization Reactions with a Picolinamide Directing Group: Ni-Catalyzed Cleavage and Byproduct Recycling

被引：16

作者：

Biswas, Sovan ^{[1
]}

Bheemireddy, Narendraprasad Reddy ^{[1
]}

Bal, Mathias ^{[1
]}

Van Steijvoort, Ben F. ^{[1
]}

Maes, Bert U. W. ^{[1
]}

机构：

[1] Univ Antwerp, Dept Chem, Organ Synth, Groenenborgerlaan 171, B-2020 Antwerp, Belgium

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2019年 / 84卷 / 20期

基金：

欧盟地平线“2020”;

关键词：

UNACTIVATED C(SP(3))-H BONDS; REMOTE FUNCTIONALIZATION; C(SP(2))-H BONDS; ACTIVATION; ARYLATION; AMIDES; CONVERSION; AMINATION; ESTERS; GAMMA;

D O I：

10.1021/acs.joc.9b02299

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An efficient strategy for the cleavage of the picolinamide directing group (DG) and recycling of the byproduct generated has been developed. In this protocol, picolinamides were first Boc activated into tertiary N-Boc-N-substituted picolinamides. These were then cleaved via a Ni-catalyzed esterification reaction with EtOH to give valuable N-Boc protected amines. Ni(cod)(2) was used as a catalyst without any ligands or base additives. The byproduct, ethyl 2-picolinate can be used to install the picolinamide DG in a direct or indirect manner on amines. The protocol exhibits a broad functional group tolerance and high yields. To demonstrate the utility of this approach, it was applied on many selected examples from the recent C-H functionalization literature featuring 2-picolinamide as a DG.

引用

页码：13112 / 13123

页数：12

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