Expanding the Ligand Framework Diversity of Carbodicarbenes and Direct Detection of Boron Activation in the Methylation of Amines with CO2

被引:144
作者
Chen, Wen-Ching [1 ]
Shen, Jiun-Shian [1 ]
Jurca, Titel [2 ]
Peng, Chun-Jung [1 ]
Lin, Yen-Hsu [1 ]
Wang, Yi-Ping [1 ]
Shih, Wei-Chih [1 ]
Yap, Glenn P. A. [3 ]
Ong, Tiow-Gan [1 ,4 ]
机构
[1] Acad Sinica, Inst Chem, Taipei, Taiwan
[2] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
[3] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA
[4] Natl Chiao Tung Univ, Dept Appl Chem, Taipei, Taiwan
关键词
carbene ligands; carbodicarbenes; CO2; activation; ligand design; organocatalysis; N-HETEROCYCLIC CARBENE; MAIN-GROUP COMPOUNDS; CARBON-DIOXIDE; H BONDS; STRUCTURAL IMPLICATIONS; COORDINATION CHEMISTRY; CATALYTIC METHYLATION; DATIVE BONDS; B-H; REDUCTION;
D O I
10.1002/anie.201507921
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A simple and convergent synthetic strategy used to increase the diversity of the carbodicarbene ligand framework through incorporation of unsymmetrical pendant groups is reported. Structural analysis and spectroscopic studies of ligands and their Rh complexes are reported. Reactivity studies reveal carbodicarbenes as competent organocatalysts for amine methylation using CO2 as a synthon. A unique B-H-activated boron-carbodicarbene complex was isolated as a reaction intermediate, providing mechanistic insight into the CO2 functionalization process.
引用
收藏
页码:15207 / 15212
页数:6
相关论文
共 78 条
  • [1] Intercepting low oxidation state main group hydrides with a nucleophilic N-heterocyclic olefin
    Al-Rafia, S. M. Ibrahim
    Malcolm, Adam C.
    Liew, Sean K.
    Ferguson, Michael J.
    McDonald, Robert
    Rivard, Eric
    [J]. CHEMICAL COMMUNICATIONS, 2011, 47 (24) : 6987 - 6989
  • [2] Chiral heterobimetallic complexes of carbodiphosphoranes and phosphinidene-carbene adducts
    Alcarazo, Manuel
    Radkowski, Karin
    Mehler, Gerlinde
    Goddard, Richard
    Fuerstner, Alois
    [J]. CHEMICAL COMMUNICATIONS, 2013, 49 (30) : 3140 - 3142
  • [3] Alcarazo M, 2009, NAT CHEM, V1, P295, DOI [10.1038/NCHEM.248, 10.1038/nchem.248]
  • [4] Anderson D. R., 2007, ANGEW CHEM, V119, P7400
  • [5] Synthesis and reactivity of olefin metathesis catalysts bearing cyclic (alkyl) (amino) carbenes
    Anderson, Donde R.
    Lavallo, Vincent
    O'Leary, Daniel J.
    Bertrand, Guy
    Grubbs, Robert H.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (38) : 7262 - 7265
  • [6] Practical Methylenation Reaction for Aldehydes and Ketones Using New Julia-Type Reagents
    Ando, Kaori
    Kobayashi, Takahisa
    Uchida, Nariaki
    [J]. ORGANIC LETTERS, 2015, 17 (10) : 2554 - 2557
  • [7] [Anonymous], 2005, ANGEW CHEM
  • [8] A STABLE CRYSTALLINE CARBENE
    ARDUENGO, AJ
    HARLOW, RL
    KLINE, M
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (01) : 361 - 363
  • [9] Aresta M., 2010, CARBON DIOXIDE CHEM
  • [10] Beydoun K., 2014, ANGEW CHEM, V126, P11190