Stereoselective metal-free catalytic synthesis of chiral trifluoromethyl aryl and alkyl amines.

The enantioselective organocatalytic reduction of trifluoromethyl aryl and alkyl ketoimines afforded the corresponding fluorinated amines with high chemical and stereochemical efficiency. The Lewis base catalyzed reaction with trichlorosilane led to chiral products with a trifluoromethyl group directly linked to the newly generated stereocenter typically in >90% yield and up to 98% e.e.

[1]  M. Benaglia,et al.  Enantioselective organocatalytic reductions , 2013 .

[2]  Jun‐An Ma,et al.  Highly enantioselective organocatalytic Strecker reaction of cyclic N-acyl trifluoromethylketimines: synthesis of anti-HIV drug DPC 083. , 2012, Chemical communications.

[3]  Yongwei Wu,et al.  Asymmetric synthesis of trifluoromethylated amines via catalytic enantioselective isomerization of imines. , 2012, Journal of the American Chemical Society.

[4]  C. J. Warner,et al.  Trichlorosilane mediated asymmetric reductions of the C=N bond. , 2012, Organic & biomolecular chemistry.

[5]  L. Bernardi,et al.  Organocatalytic trifluoromethylation of imines using phase-transfer catalysis with phenoxides. A general platform for catalytic additions of organosilanes to imines. , 2012, Chemical communications.

[6]  Jongwon Lim,et al.  Discovery of 1-amino-5H-pyrido[4,3-b]indol-4-carboxamide inhibitors of Janus kinase 2 (JAK2) for the treatment of myeloproliferative disorders. , 2011, Journal of medicinal chemistry.

[7]  T. Akiyama,et al.  Chiral phosphoric acid catalyzed transfer hydrogenation: facile synthetic access to highly optically active trifluoromethylated amines. , 2011, Angewandte Chemie.

[8]  T. Benincori,et al.  Organocatalytic Stereoselective Direct Aldol Reaction of Trifluoroethyl Thioesters , 2011 .

[9]  Jun‐An Ma,et al.  Asymmetric construction of stereogenic carbon centers featuring a trifluoromethyl group from prochiral trifluoromethylated substrates. , 2011, Chemical reviews.

[10]  D. O'Hagan Fluorine in health care: Organofluorine containing blockbuster drugs , 2010 .

[11]  Yong‐Gui Zhou,et al.  Enantioselective Pd-catalyzed hydrogenation of fluorinated imines: facile access to chiral fluorinated amines. , 2010, Organic letters.

[12]  M. Benaglia,et al.  Trichlorosilane‐Mediated Stereoselective Reduction of C=N Bonds , 2010 .

[13]  M. Todd,et al.  Can we measure catalyst efficiency in asymmetric chemical reactions? A theoretical approach , 2009, Beilstein journal of organic chemistry.

[14]  M. Benaglia,et al.  Chiral Lewis base promoted trichlorosilane reduction of ketimines. An enantioselective organocatalytic synthesis of chiral amines , 2009 .

[15]  G. Celentano,et al.  1,1'-Binaphthyldiamine-Based Lewis Bases as Readily Available and Efficient Organocatalysts for the Reduction of N-Aryl and N-Alkyl Ketimines , 2009 .

[16]  S. Rossi,et al.  Highly stereoselective metal-free catalytic reduction of imines: an easy entry to enantiomerically pure amines and natural and unnatural alpha-amino esters. , 2009, Organic letters.

[17]  F. Gosselin,et al.  A practical enantioselective synthesis of odanacatib, a potent Cathepsin K inhibitor, via triflate displacement of an alpha-trifluoromethylbenzyl triflate. , 2009, The Journal of organic chemistry.

[18]  Jun‐An Ma,et al.  Update 1 of: Asymmetric fluorination, trifluoromethylation, and perfluoroalkylation reactions. , 2008, Chemical reviews.

[19]  Jun‐An Ma,et al.  Strategies for Nucleophilic, Electrophilic, and Radical Trifluoromethylations , 2007 .

[20]  Nan Zhang,et al.  Synthesis and SAR of [1,2,4]triazolo[1,5-a]pyrimidines, a class of anticancer agents with a unique mechanism of tubulin inhibition. , 2007, Journal of medicinal chemistry.

[21]  Ann Thayer,et al.  Enzymes at Work , 2006, Science.

[22]  Y. Matsumura,et al.  New efficient organic activators for highly enantioselective reduction of aromatic ketones by trichlorosilane. , 2006, Organic letters.

[23]  H. Amii,et al.  Pd-Catalyzed Asymmetric Hydrogenation of α-Fluorinated Iminoesters in Fluorinated Alcohol: A New and Catalytic Enantioselective Synthesis of Fluoro α-Amino Acid Derivatives , 2001 .

[24]  G. Celentano,et al.  A Convenient, Highly Stereoselective,Metal-Free Synthesis of Chiral Amines , 2010 .

[25]  T. Hiyama,et al.  Modern synthetic methods for fluorine-substituted target molecules. , 2004, Angewandte Chemie.

[26]  G. Prakash,et al.  Synthesis of Chiral Trifluoromethylated Amines by Palladium‐Catalyzed Diastereoselective Hydrogenation‐Hydrogenolysis Approach , 2003 .