A Base and Solvent-Free Ruthenium-Catalyzed Alkylation of Amines

被引：71
作者：
Celaje, Jeff Joseph A.
Zhang, Xingyue
Zhang, Forrest
Kam, Lisa
Herron, Jessica R.
Williams, Travis J. [1 ]
机构：
[1] Univ Southern Calif, Donald P & Katherine B Loker Hydrocarbon Inst, Los Angeles, CA 90089 USA
来源：
ACS CATALYSIS | 2017年 / 7卷 / 02期
基金：
美国国家科学基金会;
关键词：
amination; hydrogen borrowing; catalysis; imine; dehydrogenation; BORROWING HYDROGEN METHODOLOGY; METAL-LIGAND COOPERATION; N-HETEROCYCLIC CARBENE; ASTERISK-IR COMPLEX; ONE-POT SYNTHESIS; REDUCTIVE AMINATION; SELECTIVE ALKYLATION; (HETERO)AROMATIC AMINES; EFFICIENT CATALYSTS; SECONDARY ALCOHOLS;
D O I：
10.1021/acscatal.6b03088
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：
A (pyridyl)phosphine-ligated ruthenium(II) catalyst is reported for the chemoselective benzylic N-alkylation of amines, via a hydrogen-borrowing mechanism. The catalyst operates under mild conditions, neat, and without a base or other additive. These conditions offer remarkable functional group compatibility for applications in organic synthesis, including reactions involving phenols and anilines, which are very difficult to achieve. Mechanistic studies suggest that, unlike other catalysts for this reaction, the redox steps are fast and reversible while imine formation is slow. We perceive that this is the origin of the selectivity realized with these reaction conditions.
引用
收藏
页码：1136 / 1142
页数：7
相关论文
共 158 条
[31]   Organic Ligand-Free Alkylation of Amines, Carboxamides, Sulfonamides, and Ketones by Using Alcohols Catalyzed by Heterogeneous Ag/Mo Oxides [J].
Cui, Xinjiang ;
Zhang, Yan ;
Shi, Feng ;
Deng, Youquan .
CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (03) :1021-1028
[32]   Fe(II)-catalyzed N-alkylation of sulfonamides with benzylic alcohols [J].
Cui, Xinjiang ;
Shi, Feng ;
Zhang, Yan ;
Deng, Youquan .
TETRAHEDRON LETTERS, 2010, 51 (15) :2048-2051
[33]   Copper-Catalyzed N-Alkylation of Sulfonamides with Benzylic Alcohols: Catalysis and Mechanistic Studies [J].
Cui, Xinjiang ;
Shi, Feng ;
Tse, Man Kin ;
Goerdes, Dirk ;
Thurow, Kerstin ;
Beller, Matthias ;
Deng, Youquan .
ADVANCED SYNTHESIS & CATALYSIS, 2009, 351 (17) :2949-2958
[34]   Iridium-catalysed condensation of alcohols and amines as a method for aminosugar synthesis [J].
Cumpstey, Ian ;
Agrawal, Santosh ;
Borbas, K. Eszter ;
Martin-Matute, Belen .
CHEMICAL COMMUNICATIONS, 2011, 47 (27) :7827-7829
[35]  
Dauban P., 2008, Amino Group Chemistry, P55
[36]   Clean borrowing hydrogen methodology using hydrotalcite supported copper catalyst [J].
Dixit, Manish ;
Mishra, Manish ;
Joshi, Pradyuman A. ;
Shah, Dinesh O. .
CATALYSIS COMMUNICATIONS, 2013, 33 :80-83
[37]   Dehydrogenation as a Substrate-Activating Strategy in Homogeneous Transition-Metal Catalysis [J].
Dobereiner, Graham E. ;
Crabtree, Robert H. .
CHEMICAL REVIEWS, 2010, 110 (02) :681-703
[38]   Catalytic Conversion of Ethanol into an Advanced Biofuel: Unprecedented Selectivity for n-Butanol [J].
Dowson, George R. M. ;
Haddow, Mairi F. ;
Lee, Jason ;
Wingad, Richard L. ;
Wass, Duncan F. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (34) :9005-9008
[39]   Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes [J].
Elangovan, Saravanakumar ;
Neumann, Jacob ;
Sortais, Jean-Baptiste ;
Junge, Kathrin ;
Darcel, Christophe ;
Beller, Matthias .
NATURE COMMUNICATIONS, 2016, 7
[40]   Ruthenium-Catalyzed N-Alkylation of Amines with Alcohols under Mild Conditions Using the Borrowing Hydrogen Methodology [J].
Enyong, Arrey B. ;
Moasser, Bahram .
JOURNAL OF ORGANIC CHEMISTRY, 2014, 79 (16) :7553-7563
12345678910