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Substrate-Directed Enantioselective Aziridination of Alkenyl Alcohols Controlled by a Chiral Cation

Published version
Peer-reviewed

Type

Article

Change log

Authors

Fanourakis, Alexander 
Hodson, Nicholas 
Lit, Arthur 

Abstract

Alkene aziridination is a highly versatile transformation for the construction of chiral nitrogen-containing com-pounds. Inspired by the success of analogous substrate-directed epoxidations, we report an enantioselective aziridination of alkenyl alcohols which enables asymmetric nitrene transfer to alkenes with varied substitution patterns, including those not covered by the current protocols. We believe that our method is effective because it is substrate-directed, exploiting a net-work of attractive non-covalent interactions between the substrate, an achiral dianionic rhodium(II,II) tetracarboxylate di-mer and its two associated cinchona alkaloid-derived cations. It is these cations that provide a defined chiral pocket in which the aziridination can occur. In addition to a thorough evaluation of compatible alkene classes, we advance a practical mne-monic to predict reaction outcome and disclose a range of post-functionalization protocols which highlight the unique syn-thetic potential of the enantioenriched aziridine-alcohol products.

Description

Funder: Agency for Science, Technology and Research


Funder: Cambridge Trust


Funder: Wolfson College, University of Cambridge


Funder: Engineering and Physical Sciences Research Council

Keywords

3402 Inorganic Chemistry, 3405 Organic Chemistry, 34 Chemical Sciences

Journal Title

Journal of the American Chemical Society

Conference Name

Journal ISSN

0002-7863
1520-5126

Volume Title

145

Publisher

American Chemical Society
Sponsorship
European Research Council (757381)