Cobalt(III)-Catalyzed Diastereo- and Enantioselective Three-Component C-H Functionalization

被引:48
作者
Herraiz, Ana G. [1 ]
Cramer, Nicolai [1 ]
机构
[1] Ecole Polytech Fed Lausanne EPFL, Lab Asymmetr Catalysis & Synth, Inst Chem Sci & Engn, CH-1015 Lausanne, Switzerland
基金
瑞士国家科学基金会;
关键词
asymmetric catalysis; cobalt; C-H functionalization; chiral cyclopentadienyl; multicomponent reaction; ASYMMETRIC FUNCTIONALIZATION; MULTICOMPONENT REACTIONS; BOND FUNCTIONALIZATION; ACTIVATION; CATALYSIS; LIGANDS; ALKENES; RH;
D O I
10.1021/acscatal.1c03153
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Catalytic enantioselective C-H functionalization has recently become a tool for the creation of stereogenic centers. The steep increase in molecular complexity of multicomponent reactions matches very well with asymmetric C-H functionalizations, but the realization of such processes remains a large challenge. We describe a diastereoselective and highly enantioselective three-component C-H functionalization catalyzed by an earth-abundant Co(III) complex equipped with a chiral cyclopentadienyl ligand (Cp-x). The transformation provides a rapid access to substituted beta-hydroxyketones using three readily accessible starting materials. The outlined reactivity of (CpCo)-Co-x(III) catalysis shows a higher and exploitable propensity for selective additions across carbonyls in contrast to the chemistry of Rh(III).
引用
收藏
页码:11938 / 11944
页数:7
相关论文
共 69 条
[1]   Transition Metal Catalyzed Enantioselective C(sp2)-H Bond Functionalization [J].
Achar, Tapas Kumar ;
Maiti, Sudip ;
Jana, Sadhan ;
Maiti, Debabrata .
ACS CATALYSIS, 2020, 10 (23) :13748-13793
[2]   Chiral N-Heterocyclic Carbene Ligand Enabled Nickel(0)-Catalyzed Enantioselective Three-Component Couplings as Direct Access to Silylated Indanols [J].
Ahlin, Joachim S. E. ;
Cramer, Nicolai .
ORGANIC LETTERS, 2016, 18 (13) :3242-3245
[3]   Mild complexation protocol for chiral CpxRh and Ir complexes suitable for in situ catalysis [J].
Audic, B. ;
Wodrich, M. D. ;
Cramer, N. .
CHEMICAL SCIENCE, 2019, 10 (03) :781-787
[4]   Building Complexity and Achieving Selectivity through Catalysis - Case Studies from the Pharmaceutical Pipeline [J].
Beaver, Matthew G. ;
Caille, Seb ;
Farrell, Robert P. ;
Roetheli, Andreas R. ;
Smith, Austin G. ;
Tedrow, Jason S. ;
Thiel, Oliver R. .
SYNLETT, 2021, 32 (05) :457-471
[5]   Selective and synergistic cobalt(III)-catalysed three-component C-H bond addition to dienes and aldehydes [J].
Boerth, Jeffrey A. ;
Maity, Soham ;
Williams, Sarah K. ;
Mercado, Brandon Q. ;
Ellman, Jonathan A. .
NATURE CATALYSIS, 2018, 1 (09) :673-679
[6]   A Convergent Synthesis of Functionalized Alkenyl Halides through Cobalt(III)-Catalyzed Three-Component C-H Bond Addition [J].
Boerth, Jeffrey A. ;
Ellman, Jonathan A. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (33) :9976-9980
[7]   Highly Stereoselective Cobalt(III)-Catalyzed Three-Component C-H Bond Addition Cascade [J].
Boerth, Jeffrey A. ;
Hummel, Joshua R. ;
Ellman, Jonathan A. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (41) :12650-12654
[8]   Rh(III)-catalyzed diastereoselective C-H bond addition/cyclization cascade of enone tethered aldehydes [J].
Boerth, Jeffrey A. ;
Ellman, Jonathan A. .
CHEMICAL SCIENCE, 2016, 7 (02) :1474-1479
[9]   Three-Component 1,2-Carboamidation of Bridged Bicyclic Alkenes via RhIII-Catalyzed Addition of C-H Bonds and Amidating Reagents [J].
Brandes, Daniel S. ;
Sirvent, Ana ;
Mercado, Brandon Q. ;
Ellman, Jonathan A. .
ORGANIC LETTERS, 2021, 23 (07) :2836-2840
[10]   Efficient Kinetic Resolution of Sulfur-Stereogenic Sulfoximines by Exploiting CpXRhIII-Catalyzed C-H Functionalization [J].
Brauns, Marcus ;
Cramer, Nicolai .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2019, 58 (26) :8902-8906