title: Allylic substitution on cyclopentene and -hexene rings with alkynylcopper reagents.
abstract: Substitution of cyclic allylic picolinates with a reagent derived from TMS-C≡CMgBr and a copper salt was investigated. Although the previous type of reagent (TMSC≡CMgBr and CuBr·Me(2)S) developed for linear allylic picolinates was less product selective and regioselective, the Cu(acac)(2)-derived reagent was highly selective (94-95%) to afford the S(N)2' product in good yields. As an application, several C-C bond formations at the acetylenic carbon and the synthesis of the PG intermediate were studied with success.
authors: Department of Biomolecular Engineering, Tokyo Institute of Technology, Box B52, Nagatsuta-cho 4259, Midori-ku, Yokohama 226-8501, Japan.
authors: Qian
authors: Q
authors: Wang
authors: Yuichi
authors: Y
authors: Kobayashi
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D003517:Cyclopentanes / Q000737:chemistry*; D007202:Indicators and Reagents / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D000480:Alkynes; D000498:Allyl Compounds; D003517:Cyclopentanes; D007202:Indicators and Reagents; D009942:Organometallic Compounds; D003300:Copper; C117224:1-hexene