Issue 7, 2012

A computational study of the origin of stereoinduction in NHC-catalyzed annulation reactions of α,β-unsaturated acyl azoliums

Abstract

The origin of stereoselectivity of NHC-catalyzed annulation reactions of ynals and stable enols was studied with Density Functional Theory. The data suggest that the C–C bond formation is the stereo-determining step. Only the deprotonated pathway (containing an oxy-anion and overall neutral species) was found to give rise to discrimination of the competing stereoisomers. This is due predominantly to electrostatic repulsion of the β-stabilizing enolate functionality with the π-cloud of the aryl group in the NHC-catalyst.

Graphical abstract: A computational study of the origin of stereoinduction in NHC-catalyzed annulation reactions of α,β-unsaturated acyl azoliums

Supplementary files

Article information

Article type
Edge Article
Submitted
15 Mar 2012
Accepted
22 Apr 2012
First published
24 Apr 2012

Chem. Sci., 2012,3, 2346-2350

A computational study of the origin of stereoinduction in NHC-catalyzed annulation reactions of α,β-unsaturated acyl azoliums

E. Lyngvi, J. W. Bode and F. Schoenebeck, Chem. Sci., 2012, 3, 2346 DOI: 10.1039/C2SC20331F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements