Studies towards the asymmetric total synthesis of solandelactone oxylipins: the total synthesis of solandelactone E

A stereocontrolled approach to the elaborate skeleton of the solandelactone oxylipins culminating in the total synthesis of solandelactone E in 26 steps and 0.7% overall yield from commercially available D-glyceraldehyde acetonide has been successfully developed and executed. Highlights of the synthesis include a novel diastereoselective, acetal directed cyclopropanation of an electron deficient olefin, a diastereoselective asymmetric dihydroxylation, and a stereoselective [2, 3]-sigmatropic rearrangement of a chiral selenoxide intermediate. This innovative route can be easily adapted to gain access to other oxylipins of differing carboskeletal framework.