en
Scientific article
English

Remote Functionalization of α,β-Unsaturated Carbonyls by Multimetallic Sequential Catalysis

Published inJournal of the American Chemical Society, vol. 141, no. 42, p. 16983-16990
Publication date2019
Abstract

The remote functionalization of α,β-unsaturated carbonyls by an array of multimetallic sequential catalytic systems is described. The reactions are triggered by hydrometalation using [Pd–H] or [Ru–H] isomerization catalysts and driven by the formation of thermodynamically more stable 1,2-vinyl arenes. The Pd-catalyzed deconjugative isomerization was combined with a Cu-catalyzed β-borylation of the transiently generated styrenyl derivatives to deliver a range of products that would not be accessible with the use of a single catalyst. [Pd/Cu] catalytic systems were also identified for the highly enantioselective α-hydroboration and α-hydroamination of the styrenyl intermediates. Difunctionalization simultaneously at the benzylic and homobenzylic positions was achieved by combining the isomerization process with Sharpless asymmetric dihydroxylation (SAD) using [Pd/Os] or [Ru/Os] couples. Starting from a simple α,β-unsaturated ester, an isomerization/dihydroxylation/lactonization sequence gave access to a naturally occurring γ-butyrolactone in good yield, with excellent diastereo- and enantioselectivity.

Research group
Citation (ISO format)
ROMANO, Ciro, FIORITO, Daniele, MAZET, Clement. Remote Functionalization of α,β-Unsaturated Carbonyls by Multimetallic Sequential Catalysis. In: Journal of the American Chemical Society, 2019, vol. 141, n° 42, p. 16983–16990. doi: 10.1021/jacs.9b09373
Main files (1)
Article (Published version)
accessLevelRestricted
Secondary files (1)
Identifiers
ISSN of the journal0002-7863
419views
0downloads

Technical informations

Creation10/25/2019 10:55:00 AM
First validation10/25/2019 10:55:00 AM
Update time03/15/2023 6:15:07 PM
Status update03/15/2023 6:15:06 PM
Last indexation01/17/2024 6:38:14 AM
All rights reserved by Archive ouverte UNIGE and the University of GenevaunigeBlack