Total synthesis of myriocin and mycestericin D employing Rh(II)-catalyzed C[sbnd]H amination followed by stereoselective alkylation

Total synthesis of myriocin and mycestericin D was achieved using the Du Bois Rh(II)-catalyzed C[sbnd]H amination of a sulfamate and subsequent alkylation as a key step. The reaction of a sulfamate with PhI(OAc)₂and MgO in the presence of Rh₂(OAc)₄gave oxathiazinane N,O-acetal as the sole product in high yield. Alkylation of N,O-acetal using vinylmagnesium bromide in the presence of ZnCl₂proceeded stereoselectively to provide an oxathiazinane bearing a quaternary chiral center in high yield. Myriocin and mycestericin D were synthesized from a common synthetic intermediate. This route includes the first application of the Du Bois procedure for constructing a quaternary chiral center.