A one-pot diastereoselective synthesis of cis-3-hexene-1,6-diols via an unusually reactive organozinc intermediate.J Am Chem Soc. 2003 Mar 19; 125(11):3210-1.JA
A highly diastereoselective method for the synthesis of cis-3-hexene-1,6-diols has been developed. This new reaction proceeds with excellent control of diastereoselectivity over four stereocenters and the double bond geometry. The diols are made in a one-pot procedure involving hydroboration of a terminal alkyne and transmetalation to zinc to give a divinylzinc intermediate. This intermediate undergoes reductive elimination, forming a C=C bond. In the absence of a trapping reagent, diene is liberated (70% yield); however, in the presence of ketones or aldehydes, the proposed intermediate metallocyclopentene is trapped via a double insertion of the carbonyl substrate. Workup provides the diols in 47-86% yield.