Remote stereochemical control in asymmetric Diels–Alder reactions: synthesis of the angucycline antibiotics, (−)-tetrangomycin and MM 47755

The first asymmetric syntheses of the angucycline antibiotics, (−)-tetrangomycin and MM 47755, are achieved via a short efficient sequence starting from the chiral Lewis acid promoted Diels–Alder reaction of 5-hydroxy-1,4-naphthoquinone and (±)-(E)-5-dimethylphenylsilyl-5-methyl-1-(2′-trimethylsiloxyvinyl)cyclohexene 7 where an effective kinetic resolution of the latter, controlled by its remote stereocentre, is described.