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Copper-promoted regioselective synthesis of polysubstituted pyrroles from aldehydes, amines and nitroalkenes via1,2-phenyl/alkyl migration

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posted on 2023-06-09, 11:43 authored by Dimitrios Andreou, Michael G Kallitsakis, Edouardos Loukopoulos, Catherine Gabriel, George KostakisGeorge Kostakis, Ioannis N Lykakis
The facile Copper-catalyzed synthesis of polysubstituted pyrroles from aldehydes, amines and ß-nitroalkenesis reported. Remarkably, the use of a-methyl substituted aldehydes provide efficient access to a series of tetra- and pentasubstituted pyrroles via an overwhelming 1,2-phenyl/alkyl migration. The present methodology is also accessible to non a-substituted aldehydes yielding the corresponding trisubstituted pyrroles. On the contrary, the use of ketones, in place of aldehydes, does not promote the organic transformation signifying the necessity of a-substituted aldehydes. The reaction proceeds under mild catalytic conditions with low catalyst loading (0.3 – 1 mol %), a broad scope, very good functional-group tolerance, high yields and can be easily scaled up to more than 3 mmol of product, thus highlighting a useful synthetic application of the present catalytic protocol. Based on formal kinetic studies, a possible radical pathway is proposed that involves the formation of an allylic nitrogen radical intermediate, which in turn reacts with the nitroalkene to yield the desired pyrrole framework via a radical 1,2-phenyl or alkyl migration.

History

Publication status

  • Published

File Version

  • Accepted version

Journal

Journal of Organic Chemistry

ISSN

0022-3263

Publisher

American Chemical Society

Issue

4

Volume

83

Page range

2104-2113

Department affiliated with

  • Chemistry Publications

Research groups affiliated with

  • Centre for Byzantine Cultural History Publications

Full text available

  • Yes

Peer reviewed?

  • Yes

Legacy Posted Date

2018-01-22

First Open Access (FOA) Date

2019-01-22

First Compliant Deposit (FCD) Date

2018-01-22

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