Room temperature asymmetric allylic trifluoromethylation of Morita-Baylis-Hillman carbonates.

(DHQD)(2)PHAL-catalyzed asymmetric allylic trifluoromethylation of Morita-Baylis-Hillman adducts using a Rupert-Prakash reagent is reported. This transformation provided the S(N)2' trifluoromethylated products with good yields and excellent enantioselectivities at room temperature. It was also found that the reaction could be accelerated using acetonitrile as cosolvent.

[1]  Etsuko Tokunaga,et al.  Organocatalyzed regio- and enantioselective allylic trifluoromethylation of Morita-Baylis-Hillman adducts using Ruppert-Prakash reagent. , 2011, Organic letters.

[2]  T. Ritter,et al.  Catalysis for fluorination and trifluoromethylation , 2011, Nature.

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

[4]  T. Poisson,et al.  Organocatalyzed enantioselective protonation of silyl enol ethers: scope, limitations, and application to the preparation of enantioenriched homoisoflavones. , 2010, The Journal of organic chemistry.

[5]  N. Boechat,et al.  Trifluoromethylation of Carbonyl Compounds , 2010 .

[6]  Rui Wang,et al.  Base-accelerated enantioselective substitution of Morita-Baylis-Hillman carbonates with dialkyl phosphine oxides. , 2010, Organic letters.

[7]  G. Olah,et al.  Nucleophilic perfluoroalkylation of imines and carbonyls: perfluoroalkyl sulfones as efficient perfluoroalkyl-transfer motifs. , 2010, Organic letters.

[8]  Depeng Zhao,et al.  Enantioselective construction of allylic phosphine oxides through substitution of Morita-Baylis-Hillman carbonates with phosphine oxides. , 2010, Chemical communications.

[9]  D. MacMillan,et al.  The productive merger of iodonium salts and organocatalysis: a non-photolytic approach to the enantioselective alpha-trifluoromethylation of aldehydes. , 2010, Journal of the American Chemical Society.

[10]  B. Borhan,et al.  An organocatalytic asymmetric chlorolactonization. , 2010, Journal of the American Chemical Society.

[11]  C. Barbas,et al.  Expanding the scope of cinchona alkaloid-catalyzed enantioselective alpha-aminations of oxindoles: a versatile approach to optically active 3-amino-2-oxindole derivatives. , 2009, The Journal of organic chemistry.

[12]  K. Jiang,et al.  Enantioselective Allylic Amination of Morita–Baylis–Hillman Carbonates Catalysed by Modified Cinchona Alkaloids , 2009 .

[13]  K. Jiang,et al.  Organocatalytic peroxy-asymmetric allylic alkylation. , 2009, Organic & biomolecular chemistry.

[14]  Mark E. Scott,et al.  Enantioselective alpha-trifluoromethylation of aldehydes via photoredox organocatalysis. , 2009, Journal of the American Chemical Society.

[15]  K. Jiang,et al.  Chemoselective asymmetric N-allylic alkylation of indoles with Morita-Baylis-Hillman carbonates. , 2009, Angewandte Chemie.

[16]  V. V. Levin,et al.  Nucleophilic trifluoromethylation of arylidenemalononitriles , 2008 .

[17]  W. Hagmann,et al.  The many roles for fluorine in medicinal chemistry. , 2008, Journal of medicinal chemistry.

[18]  M. Shi,et al.  Chiral phosphine-catalyzed enantioselective construction of gamma-butenolides through substitution of Morita-Baylis-Hillman acetates with 2-trimethylsilyloxy furan. , 2008, Journal of the American Chemical Society.

[19]  K. Jørgensen,et al.  Asymmetric organocatalysed [1,3]-sigmatropic rearrangements. , 2008, Chemistry.

[20]  N. Shibata,et al.  Cinchona-alkaloid-catalyzed enantioselective direct aldol-type reaction of oxindoles with ethyl trifluoropyruvate. , 2007, Angewandte Chemie.

[21]  F. Diederich,et al.  Fluorine in Pharmaceuticals: Looking Beyond Intuition , 2007, Science.

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

[23]  N. Shibata,et al.  Cinchona alkaloids/TMAF combination-catalyzed nucleophilic enantioselective trifluoromethylation of aryl ketones. , 2007, Organic letters.

[24]  A. Spek,et al.  Construction of adjacent quaternary and tertiary stereocenters via an organocatalytic allylic alkylation of Morita-Baylis-Hillman carbonates , 2007 .

[25]  N. Shibata,et al.  Lewis acid-catalyzed tri- and difluoromethylation reactions of aldehydes. , 2006, Chemical communications.

[26]  C. Cai,et al.  Trifluoromethylation of carbonyl compounds with sodium trifluoroacetate , 2005 .

[27]  Iwao Ojima,et al.  Catalytic Asymmetric Synthesis: Ojima/Asymmetric Synthesis , 2005 .

[28]  M. Krische,et al.  Regio- and stereoselective construction of gamma-butenolides through phosphine-catalyzed substitution of Morita-Baylis-Hillman acetates: an organocatalytic allylic alkylation. , 2004, Angewandte Chemie.

[29]  Hao Li,et al.  Organocatalytic enantioselective conjugate addition to alkynones. , 2004, Journal of the American Chemical Society.

[30]  L. Deng,et al.  Catalytic asymmetric cyanosilylation of ketones with chiral Lewis base. , 2003, Journal of the American Chemical Society.

[31]  A. Pfaltz,et al.  PhosphinooxazolinesA New Class of Versatile, Modular P,N-Ligands for Asymmetric Catalysis , 2000 .

[32]  R. Singh,et al.  CsF-Catalyzed Nucleophilic Trifluoromethylation of trans-Enones with Trimethyl(trifluoromethyl)silane: A Facile Synthesis of trans-α-Trifluoromethyl Allylic Alcohols , 1999 .

[33]  J. Russell,et al.  Effective nucleophilic trifluoromethylation with fluoroform and common base , 1998 .

[34]  I. Ojima,et al.  Biomedical Frontiers of Fluorine Chemistry , 1996 .

[35]  B. Smart Introduction: Fluorine Chemistry. , 1996, Chemical reviews.

[36]  M. Tozer,et al.  Methods for the synthesis of gem-difluoromethylene compounds , 1996 .

[37]  B. Trost,et al.  Asymmetric Transition Metal-Catalyzed Allylic Alkylations. , 1996, Chemical reviews.

[38]  Jens Hartung,et al.  The Osmium-Catalyzed Asymmetric Dihydroxylation: A New Ligand Class and a Process Improvement , 1992 .

[39]  R. Chambers,et al.  Direct fluorination of 1,3-dicarbonyl compounds☆☆☆ , 1996 .