NDLI: Catalytic kinetic resolution of a dynamic racemate: highly stereoselective β-lactone formation by <i>N</i>-heterocyclic carbene catalysis

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Chemical Science Vol - 5 Issue - 4

Chemical Science Vol - 5 Issue - 3

Chemical Science Vol - 5 Issue - 2

Chemical Science Vol -4

Chemical Science Vol -3

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Catalytic kinetic resolution of a dynamic racemate: highly stereoselective β-lactone formation by N-heterocyclic carbene catalysis

Content Provider	Royal Society of Chemistry (RSC)
Author	Eichman, Chad C. Johnston, Ryne C. Scheidt, Karl A. Cohen, Daniel T. Cheong, Paul Ha-Yeon
Copyright Year	2014
Abstract	This study describes the combined experimental and computational elucidation of the mechanism and origins of stereoselectivities in the NHC-catalyzed dynamic kinetic resolution (DKR) of α-substituted-β-ketoesters. Density functional theory computations reveal that the NHC-catalyzed DKR proceeds by two mechanisms, depending on the stereochemistry around the forming bond: (1) a concerted, asynchronous formal (2 + 2) aldol-lactonization process, or (2) a stepwise spiro-lactonization mechanism where the alkoxide is trapped by the NHC-catalyst. These mechanisms contrast significantly from mechanisms found and postulated in other related transformations. Conjugative stabilization of the electrophile and non-classical hydrogen bonds are key in controlling the stereoselectivity. This reaction constitutes an interesting class of DKRs in which the catalyst is responsible for the kinetic resolution to selectively and irreversibly capture an enantiomer of a substrate undergoing rapid racemization with the help of an exogenous base.
Starting Page	1974
Ending Page	1982
Page Count	9
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	5
Issue Number	5
Journal	Chemical Science
DOI	10.1039/c4sc00317a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Stereoselectivity Chemical bond Enantiomer Danish krone Racemization Density functional theory Alkoxide Stereochemistry Electrophile Hydrogen bond
Content Type	Text
Resource Type	Article
Subject	Chemistry

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Catalytic Kinetic Resolution of a Dynamic Racemate: Highly Stereoselective β-Lactone Formation by N-Heterocyclic Carbene

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