Dynamic Kinetic Resolution of Alkenyl Cyanohydrins Derived from alpha,beta-Unsaturated Aldehydes: Stereoselective Synthesis of E-Tetrasubstituted Olefins

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A novel dynamic kinetic resolution (DKR) of tetrasubstituted alkenyl cyanohydrins prepared from the corresponding alpha,beta-unsaturated aldehydes is described. The deprotonation of a geometrical mixture of tetrasubstituted alkenyl cyanohydrins with sodium diisopropylamide (NaDA) affords the allylic anions, which enables the equilibration of the E- and Z-olefins to permit the selective functionalization of the E-adduct. Theoretical studies indicate that the nature of the alkali metal cation is a critical component to lowering the barrier for inter conversion between the two geometrical isomers, which provides the mechanistic basis for the DKR reaction. In addition, we demonstrate that the DKR reaction can be combined with a transition metal-catalyzed allylic substitution to generate a stereodefined E-tetrasubstituted olefin and quaternary center in a single cross-coupling reaction.
Publisher
AMER CHEMICAL SOC
Issue Date
2019-07
Language
English
Article Type
Article
Citation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.141, no.30, pp.11770 - 11774

ISSN
0002-7863
DOI
10.1021/jacs.9b04384
URI
http://hdl.handle.net/10203/266074
Appears in Collection
CH-Journal Papers(저널논문)
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