13 Boron “Ate” Complexes for Asymmetric Synthesis

S. G. Aiken; J. M. Bateman; V. K. Aggarwal

Abstract

Addition of a nucleophile to a boronic ester results in the generation of a tetravalent boronate “ate” complex. If there is a leaving group stationed on the carbon atom α to the boron atom, the boronate complex can undergo stereospecific 1,2-migration with simultaneous expulsion of the leaving group to form a homologated boronic ester. The enantioselectivity of the process is dictated by either incorporating a chiral substituent into the boronic ester component (substrate control), or by forming a boronate complex through the addition of an enantioenriched carbenoid species to a boronic ester (reagent control). Activation of a boronic ester with organolithium reagents generates a nucleophilic boronate complex that acts as a chiral organometallic-type reagent, reacting with a wide range of electrophiles with inversion of stereochemistry. This chapter discusses methodology available for the enantioselective homologation of boronic esters using both substrate- and reagent-controlled strategies, and the development of boronate complexes as chiral nucleophiles.

Key words

Matteson reaction - substrate control - reagent control - homologation of boronic esters - asymmetric deprotonation - lithiation–borylation - 1,2-migration - 1,2-metalate rearrangement - stereospecific - assembly-line synthesis - contiguous stereocenters - chiral organometallic reagents

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