Palladium-catalyzed DYKAT of butadiene monoepoxide: enantioselective total synthesis of (+)-DMDP, (-)-bulgecinine, and (+)-broussonetine G.
Palladium catalyzed asymmetric allylic alkylation reaction of an amine with two equivalents of butadiene monoxide allows for the expedient synthesis of trans- and cis-2,5-dihydropyrroles. The versatility of these chiral synthons towards the synthesis of a wide variety of iminosugar natural products was demonstrated with the short and high yielding asymmetric syntheses of (+)-DMDP, and (-)-bulgecinine. In addition, the first total synthesis of (+)-broussonetine G, a potent glycosidase inhibitor, is described along with the assignment of its relative and absolute stereochemical configuration.
Trost
Barry M
BM
Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA. bmtrost@stanford.edu
Horne
Daniel B
DB
Woltering
Michael J
MJ
D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D000478:Alkylation; D002384:Catalysis; D004852:Epoxy Compounds / Q000737:chemistry*; D006020:Glycopeptides / Q000138:chemical synthesis* / Q000737:chemistry; D050112:Imino Pyranoses / Q000138:chemical synthesis / Q000737:chemistry; D008353:Mannitol / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D019906:Nuclear Magnetic Resonance, Biomolecular; D010165:Palladium / Q000737:chemistry; D011759:Pyrrolidines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
C494911:2,5-dideoxy-2,5-imino-D-mannitol; D000470:Alkaloids; D004852:Epoxy Compounds; D006020:Glycopeptides; D050112:Imino Pyranoses; D011759:Pyrrolidines; C113406:broussonetine G; D008353:Mannitol; C024370:3,4-epoxy-1-butene; D010165:Palladium; C036713:bulgecin