title: Catalytic Asymmetric Total Synthesis of (-)-Actinophyllic Acid.
abstract: Described herein is a catalytic asymmetric total synthesis of (-)-actinophyllic acid, with the key step being a chiral phosphine-catalyzed [3 + 2] annulation between an imine and an allenoate to form a pyrroline intermediate in 99% yield and 94% ee. The synthesis also features CuI-catalyzed coupling between a ketoester and a 2-iodoindole to shape the tetrahydroazocine ring; intramolecular alkylative lactonization; SmI2-mediated intramolecular pinacol coupling between ketone and lactone subunits to assemble the complex skeleton of (-)-actinophyllic acid; and an unprecedented regioselective dehydroxylation.
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Lingchao
authors.initials: L
authors.lastname: Cai
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Kui
authors.initials: K
authors.lastname: Zhang
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Ohyun
authors.initials: O
authors.lastname: Kwon
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry; D007097:Imines / Q000737:chemistry; D026121:Indole Alkaloids / Q000138:chemical synthesis*; D010084:Oxidation-Reduction; D010720:Phosphines / Q000737:chemistry; D011758:Pyrroles / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D007097:Imines; D026121:Indole Alkaloids; D010720:Phosphines; D011758:Pyrroles; C500686:actinophyllic acid; C013231:pyrroline; D003300:Copper