Abstract
The enol acetate 26 couples stereospecifically with the vinylic bromides 25 and 29 in the presence of tributyltin methoxide and a catalytic amount of dichlorobis(tri-o-tolylphosphine)palladium to give the βγ-unsaturated ketones 27 and 30 with retention of double-bond position and geometry. The βγ-unsaturated ketone 42 which has stereochemistry and functionality corresponding to the C(17)–C(24) fragment of the C(20)-deoxybryostatins, is similarly prepared from the enol acetate 26 and the vinylic bromide 41 and can be deprotected to give the hydroxyketone 43.

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