An asymmetric synthesis of (−)-cephalosporolide E and (+)-cephalosporolide F employing vinylogous Mukaiyama type reaction with an α-chloro sulfide, Noyori transfer hydrogenation and oxidative cyclization as the key steps is described.

A convergent synthesis of the entire carbon framework of phoslactomycin B is disclosed. An initial route aimed to create the C‐8 tetrasubstituted stereocentre through regioselective intermolecular coupling between an internal alkyne and an allyl silyl ether, adopting Trost's protocol, followed by [2,3] sigmatropic rearrangement. But this was not successful. In a second approach, a propargylic sulfide was rearranged to give an unsaturated ketone. This was then treated with lithio acetonitrile to create the C‐8 stereocentre selectively. The C‐4 and C‐5 stereocentres were introduced by a non‐Evans syn‐aldol reaction using Crimmins's protocol. The C‐9 and C‐11 carbinol centres were created by asymmetric transfer hydrogenation. The (Z,Z)‐diene moiety was introduced by partial reduction of a diyne following Hansen's modification of the Boland reduction reaction.