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

Charles P. Mikan; Aidan Matthews; Daniel Harris; Charlotte E. McIvor; Paul G. Waddell; Mark T. Sims; Jonathan P. Knowles

doi:10.1039/D3SC02303F

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

Charles P. Mikan, Aidan Matthews, Daniel Harris, Charlotte E. McIvor, Paul G. Waddell, Mark T. Sims, Jonathan P. Knowles

Applied Sciences Department

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

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Abstract

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.

Original language	English
Article number	d3sc02303f
Pages (from-to)	6992-6996
Number of pages	5
Journal	Chemical Science
Volume	14
Issue number	25
Early online date	6 Jun 2023
DOIs	https://doi.org/10.1039/D3SC02303F
Publication status	Published - 7 Jul 2023

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10.1039/D3SC02303FLicence: CC BY

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title = "Stereoselective two-carbon ring expansion of allylic amines via electronic control of palladium-promoted equilibria",

abstract = "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.",

author = "Mikan, {Charles P.} and Aidan Matthews and Daniel Harris and McIvor, {Charlotte E.} and Waddell, {Paul G.} and Sims, {Mark T.} and Knowles, {Jonathan P.}",

note = "Funding information: J. P. K. thanks the Royal Society of Chemistry for a Research Fund award (RF19-6830). C. E. M. thanks the Royal Society of Chemistry for an undergraduate research bursary.",

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T1 - Stereoselective two-carbon ring expansion of allylic amines via electronic control of palladium-promoted equilibria

AU - Mikan, Charles P.

AU - Matthews, Aidan

AU - Harris, Daniel

AU - McIvor, Charlotte E.

AU - Waddell, Paul G.

AU - Sims, Mark T.

AU - Knowles, Jonathan P.

N1 - Funding information: J. P. K. thanks the Royal Society of Chemistry for a Research Fund award (RF19-6830). C. E. M. thanks the Royal Society of Chemistry for an undergraduate research bursary.

PY - 2023/7/7

Y1 - 2023/7/7

N2 - 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.

AB - 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.

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

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