A highly active catalyst for Pd-catalyzed amination reactions: Cross-coupling reactions using aryl mesylates and the highly selective monoarylation of primary amines using aryl chlorides

被引:444
作者
Fors, Brett P. [1 ]
Watson, Donald A. [1 ]
Biscoe, Mark R. [1 ]
Buchwald, Stephen L. [1 ]
机构
[1] MIT, Dept Chem, Cambridge, MA 02139 USA
基金
美国国家卫生研究院;
关键词
D O I
10.1021/ja8055358
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A catalyst system based on a new biarylmonophosphine ligand (BrettPhos) that shows excellent reactivity for C-N cross-coupling reactions is reported. This catalyst system enables the use of aryl mesylates as a coupling partner in C-N bond-forming reactions. Additionally, the use of BrettPhos permits the highly selective monoarylation of an array of primary aliphatic amines and anilines at low catalyst loadings and with fast reaction times, including the first monoarylation of methylamine. Lastly, oxidative addition complexes of BrettPhos are included, which provide insight into the origin of reactivity for this system.
引用
收藏
页码:13552 / +
页数:4
相关论文
共 24 条
[1]   RATES AND MECHANISM OF THE FORMATION OF ZEROVALENT PALLADIUM COMPLEXES FROM MIXTURES OF PD(OAC)(2) AND TERTIARY PHOSPHINES AND THEIR REACTIVITY IN OXIDATIVE ADDITIONS [J].
AMATORE, C ;
CARRE, E ;
JUTAND, A ;
MBARKI, MA .
ORGANOMETALLICS, 1995, 14 (04) :1818-1826
[2]   Monodentate phosphines provide highly active catalysts for Pd-catalyzed C-N bond-forming reactions of heteroaromatic halides/amines and (H)N-heterocycles [J].
Anderson, Kevin W. ;
Tundel, Rachel E. ;
Ikawa, Takashi ;
Altman, Ryan A. ;
Buchwald, Stephen L. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (39) :6523-6527
[3]   Palladium-catalyzed amination of aryl nonaflates [J].
Anderson, KW ;
Mendez-Perez, M ;
Priego, J ;
Buchwald, SL .
JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (25) :9563-9573
[4]   A new class of easily activated palladium precatalysts for facile C-N cross-coupling reactions and the low temperature oxidative addition of aryl chlorides [J].
Biscoe, Mark R. ;
Fors, Brett P. ;
Buchwald, Stephen L. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (21) :6686-+
[5]   Electronic effects on the selectivity of Pd-catalyzed C-N bond-forming reactions using biarylphosphine ligands: The competitive roles of amine binding and acidity [J].
Biscoe, Mark R. ;
Barder, Timothy E. ;
Buchwald, Stephen L. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (38) :7232-7235
[6]   Palladium-mediated N-arylation of heterocyclic diamines: Insights into the origin of an unusual chemoselectivity [J].
Cabello-Sanchez, Noemi ;
Jean, Ludovic ;
Maddaluno, Jacques ;
Lasne, Marie-Claire ;
Rouden, Jacques .
JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (06) :2030-2039
[7]   Water-mediated catalyst preactivation: An efficient protocol for C-N cross-coupling reactions [J].
Fors, Brett P. ;
Krattiger, Philipp ;
Strieter, Eric ;
Buchwald, Stephen L. .
ORGANIC LETTERS, 2008, 10 (16) :3505-3508
[8]   Electronic effects on reductive elimination to form carbon-carbon and carbon-heteroatom bonds from palladium(II) complexes [J].
Hartwig, John F. .
INORGANIC CHEMISTRY, 2007, 46 (06) :1936-1947
[9]   Discovery and understanding of transition-metal-catalyzed aromatic substitution reactions [J].
Hartwig, John F. .
SYNLETT, 2006, (09) :1283-1294
[10]   Expanding Pd-catalyzed C-N bond-forming processes: The first amidation of aryl sulfonates, aqueous amination, and complementarity with Cu-catalyzed reactions [J].
Huang, XH ;
Anderson, KW ;
Zim, D ;
Jiang, L ;
Klapars, A ;
Buchwald, SL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (22) :6653-6655