Issue 8, 2013

Development of a generic activation mode: nucleophilic α-substitution of ketonesvia oxy-allyl cations

Abstract

Oxy-allyl cations have been known as transient electrophilic species since they were first proposed as intermediates in the Favorskii rearrangement in 1894. Since that time, they also have been used as a mode of activation for [4 + 3] cycloadditions in a variety of natural product syntheses. In this manuscript, we describe a method for the interception of oxy-allyl cations with a diverse range of common nucleophiles, thereby demonstrating the value of this intermediate as a generic mode of activation. This simple, mild, room temperature protocol allows for the formation of a variety of high value carbon–carbon and carbon–heteroatom bonds that are readily incorporated within a series of cyclic and acyclic ketone systems. Initial efforts into the development of an enantioselective catalytic variant are also described.

Graphical abstract: Development of a generic activation mode: nucleophilic α-substitution of ketones via oxy-allyl cations

Supplementary files

Additions and corrections

Article information

Article type
Edge Article
Submitted
08 May 2013
Accepted
10 Jun 2013
First published
11 Jun 2013

Chem. Sci., 2013,4, 3075-3079

Development of a generic activation mode: nucleophilic α-substitution of ketones via oxy-allyl cations

M. N. Vander Wal, A. K. Dilger and D. W. C. MacMillan, Chem. Sci., 2013, 4, 3075 DOI: 10.1039/C3SC51266E

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