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

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 esterifica...

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Bibliographic Details
Published in:Journal of organic chemistry 2019-10, Vol.84 (20), p.13112-13123
Main Authors: Biswas, Sovan, Bheemireddy, Narendraprasad Reddy, Bal, Mathias, Van Steijvoort, Ben F, Maes, Bert U. W
Format: Article
Language:English
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Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.9b02299