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Issue 8, 2013
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Development of a generic activation mode: nucleophilic α-substitution of ketones via oxy-allyl cations

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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

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Publication details

The article was received on 08 May 2013, accepted on 10 Jun 2013 and first published on 11 Jun 2013


Article type: Edge Article
DOI: 10.1039/C3SC51266E
Citation: Chem. Sci., 2013,4, 3075-3079
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    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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