Matteson pinanediol boronates

The two contiguous stereocenters present in the aldehyde 155 were installed in a straightforward manner and with an extremely high stereoselectivity using the dihalomethyllithium insertion method of Matteson (Scheme 3) [157]. The (-i-)-pinanediol boronic ester derivative... 

Matteson et al have studied the homologation of boronic esters with dichloromethyl lithium. The stereoselectivity of the reaction involving pinanediol boronic esters is decreased due to epimerization of the homologated product by co-produced lithium chloride. Assembling the proposed intermediate by the reaction of the dichloromethyl boronic ester with an alkyl lithium does not give the same enantioselectivity as with the previous procedure. This was thought to be associated with kinetic selectivity in the attack by the nucleophiles R and CHClJ. 

Matteson DS, Sadhu KM, Peterson ML. 99% ChiraUy selective synthesis via pinanediol boronic esters insect pheromones, diols, and an amino alcohol. J. Am. Chem. Soc. 1986 108 81(R819. 

This methodology has been developed by Matteson and coworkers, with particular emphasis on chiral boronic esters derived from pinanediol. Sequential chiral centers can be assembled by an iterative procedure with excellent enantiomeric excess at each step. The two chiral centers in eldanolide (37), for example, were assembled in this manner (Scheme 36). ... 

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