title: Catalytic Asymmetric 1,4-Addition Reactions of Simple Alkylnitriles.
abstract: The development of catalytic asymmetric carbon-carbon bond-forming reactions of alkylnitriles that do not have an activating group at the α-position, under proton-transfer conditions, is a challenging research topic. Here, we report catalytic asymmetric direct-type 1,4-addition reactions of alkylnitriles with α,β-unsaturated amides by using a catalytic amount of potassium hexamethyldisilazide (KHMDS) with a chiral macro crown ether. The desired reactions proceeded in high yields with good diastereo- and enantioselectivities. To our knowledge, this is the first example of catalytic asymmetric direct-type 1,4-addition reaction of alkylnitriles without any activating group at the α-position.
authors.affiliation: Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, Japan.
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Yamashita
authors.affiliation: Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, Japan.
authors.forename: Io
authors.initials: I
authors.lastname: Sato
authors.affiliation: Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, Japan.
authors.forename: Hirotsugu
authors.initials: H
authors.lastname: Suzuki
authors.affiliation: Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, Japan. shu_kobayashi@chem.s.u-tokyo.ac.jp.
authors.forename: Shū
authors.initials: S
authors.lastname: Kobayashi
mesh_terms: D002384:Catalysis; D006860:Hydrogen Bonding; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*
chemical_list: D009570:Nitriles
keywords: 1,4-addition; asymmetric synthesis; catalyst; nitrile; strong base