Translator Disclaimer
1 January 2006 Control of Chirality by Cations in Confined Spaces: Photooxidation of Enecarbamates Inside Zeolite Supercages
J. Sivaguru, Hideaki Saito, Marissa R. Solomon, Lakshmi S. Kaanumalle, Thomas Poon, Steffen Jockusch, Waldemar Adam, V. Ramamurthy, Yoshihisa Inoue, Nicholas J. Turro
Author Affiliations +
Abstract

On photooxygenation of the optically active Z/E enecarbamates 1 (X = i-Pr) and 2 (X = Me) equipped with the oxazolidinone chiral auxiliary in methylene-blue (MB)-incorporated, alkali-metal (M = Li, Na, K, Cs, Rb), exchanged Y-type zeolites (MY-MB), oxidative cleavage of the alkenyl functionality releases the enantiomerically enriched methyldesoxybenzoin (MDB) product. The extent (�) and/or the sense (R or S) of the stereoselectivity in the formation of the MDB product depends on the choice of the alkyl substiuent (i-Pr or Me) at the C-4 position of the oxazolidinone chiral auxiliary, the Z/E configuration of the alkene functionality in the enecarbamates, and the type of alkali metal in the zeolite. Most significantly—the highlight of this study—is the reversed sense (R or S) in the stereoselection when the photooxygenation is run in CDCl3 solution versus inside the MY-MB zeolite. As a mechanistic rationale for this novel stereochemical behavior, we propose the combined action of spatial confinement and metal-ion coordination (assessed by density-functional calculations) of the substrate within the zeolite supercage, both of which greatly reduce the freedom of the substrate and entropically manipulate the stereochemical outcome.

J. Sivaguru, Hideaki Saito, Marissa R. Solomon, Lakshmi S. Kaanumalle, Thomas Poon, Steffen Jockusch, Waldemar Adam, V. Ramamurthy, Yoshihisa Inoue, and Nicholas J. Turro "Control of Chirality by Cations in Confined Spaces: Photooxidation of Enecarbamates Inside Zeolite Supercages," Photochemistry and Photobiology 82(1), 123-131, (1 January 2006). https://doi.org/10.1562/2005-06-15-RA-573
Received: 15 June 2005; Accepted: 20 July 2005; Published: 1 January 2006
JOURNAL ARTICLE
9 PAGES

This article is only available to subscribers.
It is not available for individual sale.
+ SAVE TO MY LIBRARY

SHARE
ARTICLE IMPACT
RIGHTS & PERMISSIONS
Get copyright permission
Back to Top