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Optimization of catalyst structure for asymmetric propargylation of aldehydes with allenyltrichlorosilane

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journal contribution
posted on 16.12.2020, 11:03 by Vladimir Vaganov, Yasuaki FukazawaYasuaki Fukazawa, Nikolay S. Kondratyev, Sergei A. Shipilovskikh, Steven Wheeler, Aleksandr Rubtsov, Andrei MalkovAndrei Malkov
The design of catalysts for asymmetric propargylations remains a challenging task, with only a handful of methods providing access to enantioenriched homopropargylic alcohols. In this work, guided by previously reported computational predictions, a set of atropisomeric bipyridine N,N’-dioxides was tested as Lewis base catalysts for the asymmetric propargylation of aldehydes with trichloroallenylsilane. The catalysts are easily prepared in four simple steps starting from readily available methyl ketones. Aryl-substituted derivatives proved to be highly active and showed a high level of enantiocontrol even at 1 mol% loading. The reaction scope includes a wide range of aromatic, heteroaromatic, and unsaturated aldehydes. New computations confirm that the key stereodetermining transition state structures for the synthesized catalysts are similar to those previously reported for the model structure.

Funding

Russian Science Foundation Grant 18-73-10156 (Chemical part)

National Science Foundation Grant CHE-1665407 (Computational part)

History

School

  • Science

Department

  • Chemistry

Published in

Advanced Synthesis & Catalysis

Volume

362

Issue

23

Pages

5467 - 5474

Publisher

Wiley

Version

AM (Accepted Manuscript)

Rights holder

© Wiley

Publisher statement

This is the peer reviewed version of the following article: VAGANOV, V.Y. ... et al, 2020. Optimization of catalyst structure for asymmetric propargylation of aldehydes with allenyltrichlorosilane. Advanced Synthesis & Catalysis, 362 (23), pp.5467-5474, which has been published in final form at https://doi.org/10.1002/adsc.202000936. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.

Acceptance date

24/09/2020

Publication date

2020-10-16

Copyright date

2020

ISSN

1615-4150

eISSN

1615-4169

Language

en

Depositor

Prof Andrei Malkov Deposit date: 25 September 2020