title: Hypervalent iodine(III)-promoted intermolecular C-C coupling of vindoline with β-ketoesters and related substrates.
abstract: The regioselective intermolecular coupling reaction of vindoline with a wide range of substrates including β-ketoesters, β-diketones, β-ketoaldehydes, β-ketonitriles, malononitriles, and β-cyanoesters provides an opportunity for the synthesis of vinblastine analogues containing deep-seated changes in the upper velbanamine subunit. The transition-metal-free hypervalent iodine(III)-promoted intermolecular sp(3)/sp(2) coupling, representing a special class of selective C-H activation with direct carbon-carbon bond formation, proceeds with generation of a quaternary center capable of incorporation of the vinblastine C16' methyl ester and functionalized for subsequent divergent heterocycle introduction.
authors: Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
authors: Travis C
authors: TC
authors: Turner
authors: Kotaro
authors: K
authors: Shibayama
authors: Dale L
authors: DL
authors: Boger
mesh_terms: D004952:Esters; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis* / Q000737:chemistry; D007455:Iodine / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry; D013237:Stereoisomerism; D014747:Vinblastine / Q000031:analogs & derivatives* / Q000737:chemistry
chemical_list: D004952:Esters; D006576:Heterocyclic Compounds, 4 or More Rings; D007659:Ketones; D009570:Nitriles; C009667:vindoline; D014747:Vinblastine; D007455:Iodine