Asymmetric Arylation of Imines Catalyzed by Heterogeneous Chiral Rhodium Nanoparticles.

Asymmetric arylation of aldimines catalyzed by heterogeneous chiral rhodium nanoparticles has been developed. The reaction proceeded in aqueous media without significant decomposition of the imines by hydrolysis to afford chiral (diarylmethyl)amines in high yields with outstanding enantioselectivities. This catalyst system exhibited the highest turnover number (700) in heterogeneous catalysts reported to date for these reactions. The reusability of the catalyst was also demonstrated.

[1]  Bo Wu,et al.  Enantioselective palladium-catalyzed arylation of N-tosylarylimines with arylboronic acids using a chiral 2,2'-bipyridine ligand. , 2016, Organic & biomolecular chemistry.

[2]  G. Lin,et al.  Enantioselective Addition of Heteroarylboronates to Arylimines Catalyzed by a Rhodium-Diene Complex , 2015 .

[3]  R. Peters,et al.  Exogenous-Base-Free Palladacycle-Catalyzed Highly Enantioselective Arylation of Imines with Arylboroxines. , 2015, Angewandte Chemie.

[4]  S. Py,et al.  Enantioselective Arylation of N-Tosylimines by Phenylboronic Acid Catalysed by a Rhodium/Diene Complex: Reaction Mechanism from Density Functional Theory. , 2015, Chemistry.

[5]  G. Manolikakes,et al.  Palladium-Catalyzed Enantioselective Three-Component Synthesis of α-Substituted Amines. , 2015, Organic letters.

[6]  Shuj Kobayashi,et al.  Chiral Metal Nanoparticle Systems as Heterogeneous Catalysts beyond Homogeneous Metal Complex Catalysts for Asymmetric Addition of Arylboronic Acids to α,β-Unsaturated Carbonyl Compounds. , 2015, Journal of the American Chemical Society.

[7]  Ping Wu,et al.  Enantioselective and rapid Rh-catalyzed arylation of N-tosyl- and N-nosylaldimines in methanol. , 2014, The Journal of organic chemistry.

[8]  H. Miyamura,et al.  Chiral metal nanoparticle-catalyzed asymmetric C-C bond formation reactions. , 2014, Chemical Society reviews.

[9]  T. Snape,et al.  Chiral 1,1-diaryl compounds as important pharmacophores , 2013 .

[10]  H. Miyamura,et al.  Polymer-incarcerated chiral Rh/Ag nanoparticles for asymmetric 1,4-addition reactions of arylboronic acids to enones: remarkable effects of bimetallic structure on activity and metal leaching. , 2012, Journal of the American Chemical Society.

[11]  A. Burke,et al.  Chiral Diphosphane‐ and NHC‐Containing Ruthenium Catalysts for the Catalytic Asymmetric Arylation of Aldimines with Organoboron Reagents , 2012 .

[12]  T. Sakai,et al.  Synthesis and application of 2,6-bis(trifluoromethyl)-4-pyridyl phosphanes: the most electron-poor aryl phosphanes with moderate bulkiness. , 2011, Angewandte Chemie.

[13]  K. Tomioka,et al.  Steric influence of N-phosphorus-arylimines on the rhodium-catalyzed asymmetric arylation , 2011 .

[14]  G. Lin,et al.  Highly enantioselective arylation of N-tosylalkylaldimines catalyzed by rhodium-diene complexes. , 2011, Journal of the American Chemical Society.

[15]  R. Shintani,et al.  Design and synthesis of new chiral phosphorus-olefin bidentate ligands and their use in the rhodium-catalyzed asymmetric addition of organoboroxines to N-sulfonyl imines. , 2011, Chemical communications.

[16]  A. Burke,et al.  Advances in the Catalytic Asymmetric Arylation of Imines using Organoboron Reagents: An Approach to Chiral Arylamines , 2011 .

[17]  K. Tomioka,et al.  Rhodium-catalyzed asymmetric phenylation of N-phosphinoylarylimines with triphenylborane , 2011 .

[18]  A. Vaccari,et al.  Examples of heterogeneous catalytic processes for fine chemistry , 2011 .

[19]  Hong-yu Yang,et al.  Rhodium/diene-catalyzed asymmetric arylation of N-sulfonyl indolylimines: a new access to highly optically active α-aryl 3-indolyl-methanamines. , 2010, Chemical communications.

[20]  F. Glorius,et al.  Asymmetric nanocatalysis: N-heterocyclic carbenes as chiral modifiers of Fe3O4/Pd nanoparticles. , 2010, Angewandte Chemie.

[21]  G. Lin,et al.  C1-symmetric dicyclopentadienes as new chiral diene ligands for asymmetric rhodium-catalyzed arylation of N-tosylarylimines. , 2010, Organic letters.

[22]  H. Du,et al.  Development of binaphthyl-based chiral dienes for rhodium(I)-catalyzed asymmetric arylation of N,N-dimethylsulfamoyl-protected aldimines. , 2010, Organic letters.

[23]  M. Shi,et al.  Catalytic asymmetric addition of arylboronic acids to N-Boc imines generated in situ using C2-symmetric cationic N-heterocyclic carbenes (NHCs) Pd2+ diaquo complexes , 2010 .

[24]  A. Burke,et al.  Catalytic Enantioselective Addition of Phenylboronic Acid and Phenylboroxine to N‐Tosylimines: PdII and RhI Catalysis , 2010 .

[25]  K. Tomioka,et al.  Steric tuning of the amidomonophosphane-rhodium(I) catalyst in asymmetric addition of arylboroxines to N-phosphinoyl aldimines. , 2009, Organic letters.

[26]  K. Okamoto,et al.  Electronic and steric tuning of chiral diene ligands for rhodium-catalyzed asymmetric arylation of imines. , 2009, Chemical communications.

[27]  Yasunori Yamamoto,et al.  An N-Linked Bidentate Phosphoramidite Ligand (N-Me-BIPAM) for Rhodium-Catalyzed Asymmetric Addition of Arylboronic Acids to N-Sulfonylarylaldimines. , 2009 .

[28]  S. Schaus,et al.  Enantioselective addition of boronates to acyl imines catalyzed by chiral biphenols. , 2009, Angewandte Chemie.

[29]  M. Shi,et al.  Catalytic enantioselective arylation of N-tosylarylimines with arylboronic acids using C2-symmetric cationic N-heterocyclic carbene Pd(2+) diaquo complexes. , 2009, Organic letters.

[30]  J. Ellman,et al.  Enantioselective synthesis of alpha-aryl alkylamines by Rh-catalyzed addition reactions of arylboronic acids to aliphatic imines. , 2008, Angewandte Chemie.

[31]  J. Ellman,et al.  Catalytic Enantioselective Addition of Arylboronic Acids to N-Boc Imines Generated in Situ , 2007 .

[32]  C. Gennari,et al.  Enantioselective Rh-Catalyzed Addition of Arylboronic Acids to N-Tosylarylimines , 2007 .

[33]  G. Lin,et al.  Design of C2-symmetric tetrahydropentalenes as new chiral diene ligands for highly enantioselective Rh-catalyzed arylation of N-tosylarylimines with arylboronic acids. , 2007, Journal of the American Chemical Society.

[34]  Frank Glorius,et al.  Asymmetric heterogeneous catalysis. , 2006, Angewandte Chemie.

[35]  Qi‐Lin Zhou,et al.  Enantioselective rh-catalyzed arylation of N-tosylarylimines with arylboronic acids. , 2006, Organic letters.

[36]  C. Bolm,et al.  Catalytic asymmetric approaches towards enantiomerically enriched diarylmethanols and diarylmethylamines. , 2006, Chemical Society reviews.

[37]  B. Feringa,et al.  A ligand-library approach to the highly efficient rhodium/phosphoramidite-catalyzed asymmetric arylation of N,N-dimethylsulfamoyl-protected aldimines. , 2006, Angewandte Chemie.

[38]  Ivan Marziano,et al.  Critical assessment of pharmaceutical processes--A rationale for changing the synthetic route. , 2006, Chemical reviews.

[39]  N. Tokunaga,et al.  C2-symmetric bicyclo[3.3.1]nonadiene as a chiral ligand for rhodium-catalyzed asymmetric arylation of N-(4-nitrobenzenesulfonyl)arylimines. , 2005, Organic letters.

[40]  K. Okamoto,et al.  C2-symmetric bicyclo[2.2.2]octadienes as chiral ligands: their high performance in rhodium-catalyzed asymmetric arylation of N-tosylarylimines. , 2004, Journal of the American Chemical Society.

[41]  K. Tomioka,et al.  N-Boc-L-valine-connected amidomonophosphane rhodium(I) catalyst for asymmetric arylation of N-tosylarylimines with arylboroxines. , 2004, Journal of the American Chemical Society.

[42]  K. Philippot,et al.  A case for enantioselective allylic alkylation catalyzed by palladium nanoparticles. , 2004, Journal of the American Chemical Society.

[43]  Y. Orito,et al.  Asymmetric Hydrogenation of Methyl Benzoylformate Using Platinum-Carbon Catalysts Modified with Cinchonidine , 1979 .

[44]  Lunxiang Yin,et al.  Carbon-carbon coupling reactions catalyzed by heterogeneous palladium catalysts. , 2007, Chemical reviews.