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Download fileOptimization of catalyst structure for asymmetric propargylation of aldehydes with allenyltrichlorosilane
journal contribution
posted on 16.12.2020, 11:03 authored by Vladimir Vaganov, Yasuaki Fukazawa, Nikolay S. Kondratyev, Sergei
A. Shipilovskikh, Steven Wheeler, Aleksandr Rubtsov, Andrei MalkovAndrei MalkovThe 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
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