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1,2-redox transpositions of tertiary amides

Abstract:

Reactions capable of transposing the oxidation levels of adjacent carbon atoms enable rapid and fundamental alteration of a molecule’s reactivity. Herein, we report the 1,2-transposition of the carbon atom oxidation level in cyclic and acyclic tertiary amides, resulting in the one-pot synthesis of 1,2- and 1,3-oxygenated tertiary amines. This oxidation level transfer was facilitated by the careful orchestration of an iridium-catalyzed reduction with the functionalization of transiently formed enamine intermediates. A novel 1,2-carbonyl transposition is described, and the breadth of this redox transposition strategy has been further explored by the development of aminoalcohol and enaminone syntheses. The diverse β-functionalized amine products were shown to be multifaceted and valuable synthetic intermediates, accessing challenging biologically relevant motifs.

Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1021/jacs.3c08466

Authors


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Role:
Author
ORCID:
0000-0003-4516-0510
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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Organic Chemistry
Oxford college:
Wadham College
Role:
Author
ORCID:
0000-0003-2456-5236


Publisher:
American Chemical Society
Journal:
Journal of the American Chemical Society More from this journal
Volume:
145
Issue:
40
Pages:
21745-21751
Publication date:
2023-09-27
Acceptance date:
2023-09-27
DOI:
EISSN:
1520-5126
ISSN:
0002-7863
Pmid:
37756523


Language:
English
Keywords:
Pubs id:
1537256
Local pid:
pubs:1537256
Deposit date:
2023-10-03

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