Palladium(0) catalyzed enantioselective rearrangement of O-allylic thiocarbamates to S-allylic thiocarbamates: asymmetric synthesis of allylic thiols

摘要

The Pd(0) catalyzed rearrangement of the O-allylic thiocarbamates rac-2a, rac-2b and rac-4 in the presence of the chiral bisphosphane 5 proceeded quantitatively and gave the S-allylic thiocarbamates 6a, 6b and 7, respectively, with 91, 92 and 97% ee, respectively, in high yields. Saponification of the S-allylic thiocarbamate 7 furnished the allylic thiol 9 with 97% ee.