title: Concise Total Synthesis of (+)-Gliocladins B and C.
abstract: The first total synthesis of (+)-gliocladin B is described. Our concise and enantioselective synthesis takes advantage of a new regioselective Friedel-Crafts-based strategy to provide an efficient multigram-scale access to the C3-(3'-indolyl)hexahydropyrroloindole substructure, a molecular foundation present in a significant subset of epipolythiodiketopiperazine natural alkaloids. Our first-generation solution to (+)-gliocladin B involved the stereoselective formation of (+)-12-deoxybionectin A, a plausible biosynthetic precursor. Our synthesis clarified the C15 stereochemistry of (+)-gliocladin B and allowed its full structure confirmation. Further studies of a versatile dihydroxylated diketopiperazine provided a concise and efficient synthesis of (+)-gliocladin B as well as access to (+)-gliocladin C.
authors: Massachusetts Institute of Technology, Department of Chemistry, 77 Massachusetts Avenue 18-292, Cambridge, MA 02139-4307, USA.
authors: Nicolas
authors: N
authors: Boyer
authors: Mohammad
authors: M
authors: Movassaghi