Asymmetric organocatalytic cascade reaction of aldehydes with 2-amino-β-nitrostyrenes: synthesis of chiral tetrahydroquinolines and dihydroquinolines.

An organocatalytic enantioselective Michael addition/aza-cyclization cascade reaction of aldehydes with 2-amino-β-nitrostyrenes has been developed for the construction of fully substituted chiral tetrahydroquinolines. The reaction, promoted by diphenylprolinol TMS ether as an organocatalyst, generated the chiral tetrahydroquinolines in good to high yield with excellent diastereo- and enantioselectivities (up to >30:1 dr, >99% ee). The method also provided an alternative access to chiral 1,4-dihydroquinolines, which are difficult to synthesize by other methodologies.

[1]  Derek T. Ahneman,et al.  Enantioselective, nickel-catalyzed Suzuki cross-coupling of quinolinium ions. , 2014, Organic letters.

[2]  Wen Yang,et al.  Organocatalytic Enantioselective Cascade Aza‐Michael/Michael Addition for the Synthesis of Highly Functionalized Tetrahydroquinolines and Tetrahydrochromanoquinolines , 2013 .

[3]  Sung‐Gon Kim,et al.  Organocatalytic Enantioselective Conjugate Addition—Cyclization Domino Reactions of o‐N‐Protected Aminophenyl α,β‐Unsaturated Aldehydes. , 2013 .

[4]  Yong Huang,et al.  A highly diastereo- and enantioselective synthesis of tetrahydroquinolines: quaternary stereogenic center inversion and functionalization. , 2013, Journal of the American Chemical Society.

[5]  G. Lin,et al.  A highly efficient access to enantiopure tetrahydropyridines: dual-organocatalyst-promoted asymmetric cascade reaction. , 2013, Chemical communications.

[6]  N. Li,et al.  Organocatalytic asymmetric Michael addition of aliphatic aldehydes to indolylnitroalkenes: access to contiguous stereogenic tryptamine precursors. , 2013, The Journal of organic chemistry.

[7]  B. Wang,et al.  Organocatalytic aza-Michael-Michael cascade reactions: a flexible approach to 2,3,4-trisubstituted tetrahydroquinolines. , 2012, Chemistry.

[8]  A. Singh,et al.  Organocatalyzed stereoselective construction of N-formylpiperidines via a Michael-aza-Henry-hemiaminalization reaction cascade , 2012 .

[9]  Hao Li,et al.  An organocatalytic cascade approach toward polysubstituted quinolines and chiral 1,4-dihydroquinolines-unanticipated effect of N-protecting groups. , 2012, Angewandte Chemie.

[10]  W. Xiao,et al.  Development of cascade reactions for the concise construction of diverse heterocyclic architectures. , 2012, Accounts of chemical research.

[11]  V. McKee,et al.  Structure‐Reactivity Studies of Simple 4‐Hydroxyprolinamide Organocatalysts in the Asymmetric Michael Addition Reaction of Aldehydes to Nitroolefins , 2012 .

[12]  Huifen Ng,et al.  Highly enantioselective assembly of functionalized tetrahydroquinolines with creation of an all-carbon quaternary center. , 2012, Chemistry.

[13]  M. Nishizawa,et al.  Hg(OTf)2-catalyzed vinylogous semi-pinacol rearrangement leading to 1,4-dihydroquinolines. , 2012, Organic letters.

[14]  H. Pellissier.  Recent Developments in Asymmetric Organocatalytic Domino Reactions , 2012 .

[15]  L. Gong,et al.  Step-economical synthesis of tetrahydroquinolines by asymmetric relay catalytic Friedländer condensation/transfer hydrogenation. , 2012, Angewandte Chemie.

[16]  K. Jørgensen,et al.  A simple recipe for sophisticated cocktails: organocatalytic one-pot reactions--concept, nomenclature, and future perspectives. , 2011, Angewandte Chemie.

[17]  Jieping Zhu,et al.  Chiral phosphoric acid-catalyzed enantioselective three-component Povarov reaction using enecarbamates as dienophiles: highly diastereo- and enantioselective synthesis of substituted 4-aminotetrahydroquinolines. , 2011, Journal of the American Chemical Society.

[18]  J. Menéndez,et al.  Advances in the chemistry of tetrahydroquinolines. , 2011, Chemical reviews.

[19]  D. Ramachary,et al.  A general approach to high-yielding asymmetric synthesis of chiral 3-alkyl-4-nitromethylchromans via cascade Barbas-Michael and acetalization reactions. , 2011, Organic & biomolecular chemistry.

[20]  T. Akiyama,et al.  Selective activation of enantiotopic C(sp3)-hydrogen by means of chiral phosphoric acid: asymmetric synthesis of tetrahydroquinoline derivatives. , 2011, Journal of the American Chemical Society.

[21]  K. Jørgensen,et al.  An asymmetric organocatalytic one-pot strategy to octahydroacridines. , 2011, Angewandte Chemie.

[22]  Peng‐Fei Xu,et al.  Highly enantioselective synthesis of polysubstituted tetrahydroquinolines via organocatalytic Michael/Aza-Henry tandem reactions. , 2011, Organic letters.

[23]  B. Hong,et al.  Enantioselective organocatalytic domino Michael-acetalization-Henry reactions of 2-hydroxynitrostyrene and aldehyde for the synthesis of tetrahydro-6H-benzo[c]chromenones. , 2011, Organic & biomolecular chemistry.

[24]  D. Enders,et al.  Asymmetric Synthesis of cis‐3,4‐Disubstituted Chromans and Dihydrocoumarins via an Organocatalytic Michael Addition/ Hemiacetalization Reaction , 2010 .

[25]  C. Barbas,et al.  One-pot enantioselective syntheses of iminosugar derivatives using organocatalytic anti-michael-anti-aza-Henry reactions. , 2010, Organic letters.

[26]  Y. Hayashi,et al.  Enantio- and diastereoselective synthesis of piperidines by coupling of four components in a "one-pot" sequence involving diphenylprolinol silyl ether mediated Michael reaction. , 2010, Organic letters.

[27]  Yixin Lu,et al.  Bifunctional thiourea-promoted cascade aza-Michael-Henry-dehydration reactions: asymmetric preparation of 3-nitro-1,2-dihydroquinolines. , 2010, Organic & biomolecular chemistry.

[28]  Yajun Li,et al.  Organocatalytic asymmetric tandem Michael addition-hemiacetalization: a route to chiral dihydrocoumarins, chromanes, and 4H-chromenes. , 2010, The Journal of organic chemistry.

[29]  Sun Mi Kim,et al.  Enantioselective organocatalytic C-H bond functionalization via tandem 1,5-hydride transfer/ring closure: asymmetric synthesis of tetrahydroquinolines. , 2010, Journal of the American Chemical Society.

[30]  Lili Lin,et al.  Asymmetric three-component inverse electron-demand aza-Diels-Alder reaction: efficient synthesis of ring-fused tetrahydroquinolines. , 2010, Angewandte Chemie.

[31]  D. Dixon,et al.  Multiple-organocatalyst-promoted cascade reaction: a fast and efficient entry into fully substituted piperidines. , 2010, Chemistry.

[32]  Dominique Schols,et al.  Discovery of novel small molecule orally bioavailable C-X-C chemokine receptor 4 antagonists that are potent inhibitors of T-tropic (X4) HIV-1 replication. , 2010, Journal of medicinal chemistry.

[33]  D. Enders,et al.  Organocatalytic cascade reactions as a new tool in total synthesis. , 2010, Nature chemistry.

[34]  Y. Tao,et al.  Asymmetric Cooperative Catalysis of Strong Brønsted Acid–Promoted Reactions Using Chiral Ureas , 2010, Science.

[35]  L. Maes,et al.  Antitrypanosomal activity of 1,2-dihydroquinolin-6-ols and their ester derivatives. , 2010, Journal of medicinal chemistry.

[36]  S. Chandrasekhar,et al.  The first synthesis of 2-amino-1,4-dihydroquinolines , 2009 .

[37]  S. Ji,et al.  Nano‐Iron Oxide as a Recyclable Catalyst for Intramolecular C ? N Cross‐Coupling Reactions under Ligand‐Free Conditions: One‐Pot Synthesis of 1,4‐Dihydroquinoline Derivatives , 2009 .

[38]  L. Barré,et al.  Synthesis, radiosynthesis and biological evaluation of 1,4-dihydroquinoline derivatives as new carriers for specific brain delivery. , 2009, Organic & biomolecular chemistry.

[39]  K. Jørgensen,et al.  Organocatalysis--after the gold rush. , 2009, Chemical Society reviews.

[40]  A. Headley,et al.  Di(methylimidazole)prolinol silyl ether catalyzed highly Michael addition of aldehydes to nitroolefins in water. , 2009, Organic letters.

[41]  M. Raghunathan,et al.  Synthesis and antibacterial property of quinolines with potent DNA gyrase activity. , 2009, Bioorganic & medicinal chemistry.

[42]  C. del Pozo,et al.  Organocatalytic approach to benzofused nitrogen-containing heterocycles: enantioselective total synthesis of (+)-angustureine. , 2008, Chemistry.

[43]  H. Hsieh,et al.  Discovery of 4-amino and 4-hydroxy-1-aroylindoles as potent tubulin polymerization inhibitors. , 2008, Journal of medicinal chemistry.

[44]  Y. Hayashi,et al.  Asymmetric Michael reaction of acetaldehyde catalyzed by diphenylprolinol silyl ether. , 2008, Angewandte Chemie.

[45]  B. List,et al.  Catalytic asymmetric Michael reactions of acetaldehyde. , 2008, Angewandte Chemie.

[46]  Alessandro Massi,et al.  Asymmetric organocatalysis: from infancy to adolescence. , 2008, Angewandte Chemie.

[47]  Xinhong Yu,et al.  Organocatalysis: asymmetric cascade reactions catalysed by chiral secondary amines. , 2008, Organic & biomolecular chemistry.

[48]  Shouyun Yu,et al.  Highly efficient catalytic system for enantioselective Michael addition of aldehydes to nitroalkenes in water. , 2008, Angewandte Chemie.

[49]  S. Mukherjee,et al.  Asymmetric enamine catalysis. , 2007, Chemical reviews.

[50]  Yong‐Gui Zhou.  Asymmetric hydrogenation of heteroaromatic compounds. , 2007, Accounts of chemical research.

[51]  D. Enders,et al.  Asymmetric organocatalytic domino reactions. , 2007, Angewandte Chemie.

[52]  Hao Li,et al.  Chiral Diphenylprolinol TES Ether Promoted Conjugate Addition−Aldol-Dehydration Reactions between α,β-Unsaturated Aldehydes and 2-N-Protected Amino Benzaldehydes , 2007 .

[53]  K C Nicolaou,et al.  Cascade reactions in total synthesis. , 2006, Angewandte Chemie.

[54]  D. O’Shea,et al.  Regioselective carbolithiation of o-amino-(E)-stilbenes: cascade route to the quinoline scaffold. , 2006, Organic letters.

[55]  M. Rueping,et al.  A highly enantioselective Brønsted acid catalyzed cascade reaction: organocatalytic transfer hydrogenation of quinolines and their application in the synthesis of alkaloids. , 2006, Angewandte Chemie.

[56]  H. Pellissier.  Asymmetric domino reactions. Part B: Reactions based on the use of chiral catalysts and biocatalysts , 2006 .

[57]  Y. Hayashi,et al.  Diphenylprolinol silyl ethers as efficient organocatalysts for the asymmetric Michael reaction of aldehydes and nitroalkenes. , 2005, Angewandte Chemie.

[58]  T. Roca,et al.  Sequential N-acylamide methylenation–enamide ring-closing metathesis: a synthetic entry to 1,4-dihydroquinolines , 2005 .

[59]  A. Alexakis,et al.  Enantioselective addition of organolithium reagents to quinoline catalyzed by 1,2-diamines , 2005 .

[60]  H. Malinakova,et al.  Mechanism of stereoinduction in asymmetric synthesis of highly functionalized 1,2-dihydroquinolines and 2H-1-benzopyrans via nonracemic palladacycles with a metal-bonded stereogenic carbon. , 2004, The Journal of organic chemistry.

[61]  P. Pohlhaus,et al.  Lewis acid-promoted carbon-carbon bond cleavage of aziridines: divergent cycloaddition pathways of the derived ylides. , 2004, Journal of the American Chemical Society.

[62]  S. Pastine,et al.  Pt(IV)-catalyzed cyclization of arene–alkyne substrates via C–H bond functionalization , 2003 .

[63]  C. Tratrat,et al.  A multicomponent reaction for the one-pot synthesis of 4-aza-2,3-didehydropodophyllotoxin and derivatives. , 2002, Organic letters.

[64]  S. Elmore,et al.  Nonsteroidal selective glucocorticoid modulators: the effect of C-5 alkyl substitution on the transcriptional activation/repression profile of 2,5-dihydro-10-methoxy-2,2,4-trimethyl-1H-[1]benzopyrano[3,4-f]quinolines. , 2001, Journal of medicinal chemistry.

[65]  Evans Pa,et al.  Regioselective and enantiospecific rhodium-catalyzed allylic amination with N-(arylsulfonyl)anilines. , 2001 .

[66]  R. Enriz,et al.  Inhibitors of the fungal cell wall. Synthesis of 4-aryl-4-N-arylamine-1-butenes and related compounds with inhibitory activities on beta(1-3) glucan and chitin synthases. , 2000, Bioorganic & medicinal chemistry.

[67]  J. Hunt,et al.  3-Imidazolylmethylaminophenylsulfonyltetrahydroquinolines, a novel series of farnesyltransferase inhibitors. , 2000, Bioorganic & medicinal chemistry letters.

[68]  A. Alexakis,et al.  Asymmetric synthesis of 1,2- and 1,4-dihydroquinolines , 1999 .

[69]  A. V. Varlamov,et al.  Some aspects of reduced quinoline chemistry , 1998 .

[70]  A. Katritzky,et al.  Recent progress in the synthesis of 1,2,3,4,-tetrahydroquinolines , 1996 .