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Visible-light excitation of iminium ions enables the enantioselective catalytic β-alkylation of enals

Silvi, Mattia; Verrier, Charlie; Rey, Yannick P.; Buzzetti, Luca; Melchiorre, Paolo

Authors

Charlie Verrier

Yannick P. Rey

Luca Buzzetti

Paolo Melchiorre



Abstract

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved. Chiral iminium ions - generated upon condensation of α,β-unsaturated aldehydes and amine catalysts - are used extensively by chemists to make chiral molecules in enantioenriched form. In contrast, their potential to absorb light and promote stereocontrolled photochemical processes remains unexplored. This is despite the fact that visible-light absorption by iminium ions is a naturally occurring event that triggers the mechanism of vision in higher organisms. Herein we demonstrate that the direct excitation of chiral iminium ions can unlock unconventional reaction pathways, enabling enantioselective catalytic photochemical β-alkylations of enals that cannot be realized via thermal activation. The chemistry uses readily available alkyl silanes, which are recalcitrant to classical conjugate additions, and occurs under illumination by visible-light-emitting diodes. Crucial to success was the design of a chiral amine catalyst with well-tailored electronic properties that can generate a photo-active iminium ion while providing the source of stereochemical induction. This strategy is expected to offer new opportunities for reaction design in the field of enantioselective catalytic photochemistry.

Citation

Silvi, M., Verrier, C., Rey, Y. P., Buzzetti, L., & Melchiorre, P. (2017). Visible-light excitation of iminium ions enables the enantioselective catalytic β-alkylation of enals. Nature Chemistry, 9(9), 868-873. https://doi.org/10.1038/nchem.2748

Journal Article Type Article
Acceptance Date Feb 7, 2017
Online Publication Date Mar 20, 2017
Publication Date 2017-09
Deposit Date Jan 29, 2020
Journal Nature Chemistry
Print ISSN 1755-4330
Electronic ISSN 1755-4349
Publisher Nature Publishing Group
Peer Reviewed Peer Reviewed
Volume 9
Issue 9
Pages 868-873
DOI https://doi.org/10.1038/nchem.2748
Public URL https://nottingham-repository.worktribe.com/output/3826268
Publisher URL https://www.nature.com/articles/nchem.2748
Additional Information Received: 20 September 2016; Accepted: 7 February 2017; First Online: 20 March 2017; : The authors declare no competing financial interests.