Stereoselective synthesis of the C1–C20 segment of the microsclerodermins A and B

An enantioselective route for the synthesis of key fragment C1–C20 resident in microsclerodermins A and B is described. The route features deoxygenative rearrangement of an hydroxy-alkynoate and a highly enantio- and diastereo-controled iterative dihydroxylation as key reactions, starting from S-(−)-citronellol.