title: Enantioselective synthesis of allenylenol silyl ethers via chiral lithium amide mediated reduction of ynenoyl silanes and their Diels-Alder reactions.
abstract: An enantioselective Meerwein-Ponndorf-Verley-type reduction of ynenoylsilanes by a chiral lithium amide followed by a Brook rearrangement and anti-mode protonation across conjugated 1,3-enynes provides allene derivatives bearing a 2-siloxyvinyl moiety in high enantioselectivity. The E/Z geometry of enol silyl ethers is controlled by the geometry of the starting enyne moiety. Thus, (E)- and (Z)-enol silyl ethers are obtained from (Z)- and (E)-ynenoylsilans, respectively. The 2-siloxyvinylallene products can participate in Diels-Alder reactions with reactive dienophiles such as PTAD, which can be achieved in a one-pot operation from ynenoylsilanes.
authors.affiliation: Department of Synthetic Organic Chemistry, Institute of Biomedical & Health Sciences, Hiroshima University , 1-2-3 Kasumi, Minami-Ku, Hiroshima 734-8553, Japan.
authors.forename: Michiko
authors.initials: M
authors.lastname: Sasaki
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Kondo
authors.forename: Ta-ichi
authors.initials: T
authors.lastname: Moto-ishi
authors.forename: Masatoshi
authors.initials: M
authors.lastname: Kawahata
authors.forename: Kentaro
authors.initials: K
authors.lastname: Yamaguchi
authors.forename: Kei
authors.initials: K
authors.lastname: Takeda
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D061565:Cycloaddition Reaction; D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry*; D008094:Lithium; D015394:Molecular Structure; D010084:Oxidation-Reduction; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: C000601774:2-siloxyvinylallene; D000475:Alkenes; D000577:Amides; D004987:Ethers; D012821:Silanes; D014753:Vinyl Compounds; D008094:Lithium