Total synthesis of myriocin and mycestericin D employing Rh(II)-catalyzed CH amination followed by stereoselective alkylation

Abstract Total synthesis of myriocin and mycestericin D was achieved using the Du Bois Rh(II)-catalyzed C H amination of a sulfamate and subsequent alkylation as a key step. The reaction of a sulfamate with PhI(OAc) 2 and MgO in the presence of Rh 2 (OAc) 4 gave oxathiazinane N , O -acetal as the sole product in high yield. Alkylation of N , O -acetal using vinylmagnesium bromide in the presence of ZnCl 2 proceeded 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.