Reactions at the end of a tether

Abstract

A remarkable reaction that reverses the chemical behaviour of molecules known as 1,3-diketones allows a new strategy that could be used to prepare a range of potentially useful, naturally occurring compounds. See Letter p.86 The enantioselective allylation of ketones represents a problem of fundamental importance in asymmetric reaction design, especially given that only a very small number of methods can generate tertiary carbinols. In this manuscript, the authors describe a simple, regioselective and enantioselective method for allylating β-diketones. This reaction significantly expands the pool of enantiomerically enriched and functionally complex tertiary carbinols that can be easily accessed and also overturns more than a century of received wisdom regarding the reactivity of β-diketones.