Kinetic Resolution of Tertiary Propargylic Alcohols by Enantioselective Cu-H-Catalyzed Si-O Coupling

被引：52
作者：
Seliger, Jan [1 ]
Dong, Xichang [1 ]
Oestreich, Martin [1 ]
机构：
[1] Tech Univ Berlin, Inst Chem, Str 17 Juni 115, D-10623 Berlin, Germany
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 07期
关键词：
asymmetric catalysis; copper; dehydrogenative coupling; silicon; tertiary alcohols; ASYMMETRIC-SYNTHESIS; ALKYNYL KETONES; SILYLATION; SECONDARY; EFFICIENCY; SCOPE;
D O I：
10.1002/anie.201813229
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A broad range of tertiary propargylic alcohols were kinetically resolved by catalyst-controlled enantioselective silylation. This non-enzymatic kinetic resolution is catalyzed by a Cu-H species and makes use of the commercially available precatalyst MesCu/(R,R)-Ph-BPE and a simple hydrosilane as the resolving reagent. Both alkyl,aryl- as well as dialkyl-substituted propargylic alcohols participate, and especially high selectivity factors are achieved when the alkyne terminus carries a TIPS group, which also enables facile post-functionalization in this position (s up to 207).
引用
收藏
页码：1970 / 1974
页数：5
相关论文
共 60 条
  • [1] [Anonymous], 2015, ANGEW CHEM, V127, P9590
  • [2] [Anonymous], 2005, ANGEW CHEM, V117, P4040
  • [3] Asymmetric Synthesis of Tertiary Benzylic Alcohols
    Antczak, Monika I.
    Cai, Feng
    Ready, Joseph M.
    [J]. ORGANIC LETTERS, 2011, 13 (02) : 184 - 187
  • [4] Bartsch S., 2008, ANGEW CHEM, V120, P1531
  • [5] Complete inversion of enantioselectivity towards acetylated tertiary alcohols by a double mutant of a Bacillus subtilis esterase
    Bartsch, Sebastian
    Kourist, Robert
    Bornscheuer, Uwe T.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (08) : 1508 - 1511
  • [6] Recent developments in asymmetric alkynylations
    Bisai, Vishnumaya
    Singh, Vinod K.
    [J]. TETRAHEDRON LETTERS, 2016, 57 (43) : 4771 - 4784
  • [7] Cook A. M., 2016, ANGEW CHEM, V128, P2982
  • [8] Efficient Access to Multifunctional Trifluoromethyl Alcohols through Base-Free Catalytic Asymmetric C-C Bond Formation with Terminal Ynamides
    Cook, Andrea M.
    Wolf, Christian
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (08) : 2925 - 2929
  • [9] Cozzi P. G., 2003, ANGEW CHEM, V115, P3001
  • [10] Enantioselective alkynylation of ketones catalyzed by Zn(salen) complexes
    Cozzi, PG
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (25) : 2895 - 2898
123456