Enantioselective Functionalization of Difluorocyclopropenes Catalyzed by Chiral Copper Complexes: Proposal for Chiral gem-Dimethyl and tert-Butyl Analogues

被引：27
作者：
Sekine, Keisuke [1 ]
Ushiyama, Aina [1 ]
Endo, Yu [1 ]
Mikami, Koichi [1 ]
机构：
[1] Tokyo Inst Technol, Sch Mat & Chem Technol, Dept Chem Sci & Engn, Tokyo 1528552, Japan
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2020年 / 85卷 / 12期
基金：
日本科学技术振兴机构;
关键词：
BUILDING-BLOCKS; EFFICIENT SYNTHESIS; DIFLUOROCARBENE; FLUORINE; CARBOMETALATION; CYCLOPROPANES; ALKENES; REAGENT;
D O I：
10.1021/acs.joc.0c00622
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The highly enantioselective copper/chiral phosphine-catalyzed hydro-, bora-, and carbo-metalations of difluorocyclopropenes with PHMS [H-Si], H-BPin, (BPin)(2), and (CH3)(2)Zn [Zn-Me] are shown to regiodivergently afford highly enantioenriched and functionalized difluorocyclopropanes. These examples can be viewed as the first successful syntheses of "chiral" gem-dimethyl and tert-butyl analogues.
引用
收藏
页码：7916 / 7924
页数：9
相关论文
共 44 条
  • [1] Development of (Trifluoromethyl)zinc Reagent as Trifluoromethyl Anion and Difluorocarbene Sources
    Aikawa, Kohsuke
    Toya, Wataru
    Nakamura, Yuzo
    Mikami, Koichi
    [J]. ORGANIC LETTERS, 2015, 17 (20) : 4996 - 4999
  • [2] Metabolically Stable tert-Butyl Replacement
    Barnes-Seeman, David
    Jain, Monish
    Bell, Leslie
    Ferreira, Suzie
    Cohen, Scott
    Chen, Xiao-Hui
    Amin, Jakal
    Snodgrass, Brad
    Hatsis, Panos
    [J]. ACS MEDICINAL CHEMISTRY LETTERS, 2013, 4 (06): : 514 - 516
  • [3] BIRCHALL JM, 1960, P CHEM SOC LONDON, P81
  • [4] Fluorinated carbenes
    Brahms, DLS
    Dailey, WP
    [J]. CHEMICAL REVIEWS, 1996, 96 (05) : 1585 - 1632
  • [5] SIMPLIFIED, ONE-POT PROCEDURE FOR THE SYNTHESIS OF [(PH3P)CUH]6, A STABLE COPPER HYDRIDE FOR CONJUGATE REDUCTIONS
    BRESTENSKY, DM
    HUSELAND, DE
    MCGETTIGAN, C
    STRYKER, JM
    [J]. TETRAHEDRON LETTERS, 1988, 29 (31) : 3749 - 3752
  • [6] Oxetanes as Versatile Elements in Drug Discovery and Synthesis
    Burkhard, Johannes A.
    Wuitschik, Georg
    Rogers-Evans, Mark
    Mueller, Klaus
    Carreira, Erick M.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (48) : 9052 - 9067
  • [7] Synthesis of Functionalized Difluorocyclopropanes: Unique Building Blocks for Drug Discovery
    Bychek, Roman M.
    Levterov, Vadym V.
    Sadkova, Iryna V.
    Tolmachev, Andrey A.
    Mykhailiuk, Pavel K.
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 2018, 24 (47) : 12291 - 12297
  • [8] Asymmetric hydrofunctionalization of minimally functionalized alkenes via earth abundant transition metal catalysis
    Chen, Jianhui
    Lu, Zhan
    [J]. ORGANIC CHEMISTRY FRONTIERS, 2018, 5 (02): : 260 - 272
  • [9] COREY EJ, 1972, TETRAHEDRON LETT, P3769
  • [10] Asymmetric Preparation of Polysubstituted Cyclopropanes Based on Direct Functionalization of Achiral Three-Membered Carbocycles
    Dian, Longyang
    Marek, Ilan
    [J]. CHEMICAL REVIEWS, 2018, 118 (18) : 8415 - 8434
12345