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Total synthesis of myriocin and mycestericin D was achieved using the Du Bois Rh(II)-catalyzed CH 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 Rh2(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 ZnCl2 proceeded stereoselectively...
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