Stereospecific Substitution of Allylic Alcohols To Give Optically Active Primary Allylic Amines: Unique Reactivity of a (P,alkene)Ir Complex Modulated by Iodide

被引:145
作者
Roggen, Markus [1 ]
Carreira, Erick M. [1 ]
机构
[1] ETH, Organ Chem Lab, CH-8093 Zurich, Switzerland
关键词
ENANTIOSELECTIVE SYNTHESIS; ASYMMETRIC CATALYSIS; AMINATION; LIGANDS; PHOSPHORAMIDITE; ALKYLATION; RHODIUM; ESTERS; REGIOSELECTIVITY; HYDROGENATION;
D O I
10.1021/ja105271z
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A stereospecific allylic amination of unactivated secondary (2 degrees)-allylic alcohols is reported. The primary (1 degrees)-allylic amine can be isolated directly or protected in situ. Spectroscopic studies have shed light on the structure of the catalytically active Ir.(P,olefin)2I complex.
引用
收藏
页码:11917 / 11919
页数:3
相关论文
共 50 条
[1]   Highly enantioselective hydrogenation of aryl vinyl ketones to allylic alcohols catalyzed by the tol-binap/dmapen ruthenium(II) complex [J].
Arai, Noriyoshi ;
Azuma, Keita ;
Nii, Noriyuki ;
Ohkuma, Takeshi .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (39) :7457-7460
[2]  
Bartels B, 2002, EUR J INORG CHEM, P2569
[3]   Ir-catalysed allylic substitution: mechanistic aspects and asymmetric synthesis with phosphorus amidites as ligands [J].
Bartels, B ;
Helmchen, G .
CHEMICAL COMMUNICATIONS, 1999, (08) :741-742
[4]  
BEKOWITZ DB, 2004, ORG LETT, V6, P2661
[5]   Catalytic enantioselective addition of dialkylzinc to N-diphenylphosphinoylimines.: A practical synthesis of α-chiral amines [J].
Boezio, AA ;
Charette, AB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (07) :1692-1693
[6]   Chemoenzymatic dynamic kinetic resolution of allylic alcohols:: A highly enantioselective route to acyloin acetates [J].
Bogar, Krisztian ;
Vidal, Pilar Hoyos ;
Leon, Andres R. Alcantara ;
Backvall, Jan-E. .
ORGANIC LETTERS, 2007, 9 (17) :3401-3404
[7]   Thermodynamic and kinetic data for adduct formation, cis-trans isomerization and redox reactions of ML4 complexes:: A case study with rhodium- and iridium-tropp complexes in d8, d9 and d10 valence electron configurations (tropp = dibenzotropylidene phosphanes) [J].
Breher, F ;
Rüegger, H ;
Mlakar, M ;
Rudolph, M ;
Deblon, S ;
Schönberg, H ;
Boulmaâz, S ;
Thomaier, J ;
Grützmacher, H .
CHEMISTRY-A EUROPEAN JOURNAL, 2004, 10 (03) :641-653
[8]   Chiral olefins as steering ligands in asymmetric catalysis [J].
Defieber, Christian ;
Gruetzmacher, Hansjoerg ;
Carreira, Erick M. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (24) :4482-4502
[9]   Iridium-catalyzed synthesis of primary allylic amines from allylic alcohols: Sulfamic acid as amonia equivalent [J].
Defieber, Christian ;
Ariger, Martin A. ;
Moriel, Patricia ;
Carreira, Erick M. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (17) :3139-3143
[10]   On the Absolute Configurational Stability of Bromonium and Chloronium Ions [J].
Denmark, Scott E. ;
Burk, Matthew T. ;
Hoover, Andrew J. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (04) :1232-+