Stereoselective two-carbon ring expansion of allylic amines via electronic control of palladium-promoted equilibria

General methodologies enabling the two-carbon homologation of pyrrolidine and piperidine systems have yet to be developed. Herein we report that palladium-catalysed allylic amine rearrangements enable efficient two-carbon ring expansion of 2-alkenyl pyrrolidine and piperidines to their azepane and a...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2023-06, Vol.14 (25), p.6992-6996
Main Authors: Mikan, Charles P, Matthews, Aidan, Harris, Daniel, McIvor, Charlotte E, Waddell, Paul G, Sims, Mark T, Knowles, Jonathan P
Format: Article
Language:English
Subjects:
Amines
Carbon
Chemistry
Electronic control
Functional groups
Palladium
Piperidine
Stereoselectivity
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Summary:General methodologies enabling the two-carbon homologation of pyrrolidine and piperidine systems have yet to be developed. Herein we report that palladium-catalysed allylic amine rearrangements enable efficient two-carbon ring expansion of 2-alkenyl pyrrolidine and piperidines to their azepane and azocane counterparts. Conditions are mild, tolerant of a range of functional groups and the process can occur with high enantioretention. The products formed undergo a range of orthogonal transformations, making them ideal scaffolds for the creation of compound libraries.
ISSN:2041-6520
2041-6539
DOI:10.1039/d3sc02303f