Catalytic Asymmetric Synthesis of 2‐Alkyleneoxetanes through [2+2] Annulation of Allenoates with Trifluoromethyl Ketones

The first example of a β-isocupreidine (β-ICD)-catalyzed highly enantioselective [2+2] annulation of allenoates with trifluoromethyl ketones has been disclosed, allowing the synthesis of optically active 2-alkyleneoxetanes in moderate to good yields along with good to high enantioselectivities and high diastereoselectivities. Further transformations of the cycloadducts have been also disclosed to afford biologically interesting 6-trifluoromethyl-5,6-dihydropyran-2-ones and trifluoromethyl β-keto acids in good yields.

[1]  L. Gong,et al.  A chiral bis(betaine) catalyst for the Mannich reaction of azlactones and aliphatic imines. , 2012, Angewandte Chemie.

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

[3]  K. Asano,et al.  Asymmetric synthesis of 1,3-dioxolanes by organocatalytic formal [3 + 2] cycloaddition via hemiacetal intermediates. , 2012, Organic letters.

[4]  Bin Wu,et al.  Highly Enantioselective Synthesis of Spiro[cyclohexanone-oxindoles] and Spiro[cyclohexanone-pyrazolones] by Asymmetric Cascade [5+1] Double Michael Reactions , 2012 .

[5]  Shoulei Wang,et al.  Bifunctional organocatalytic strategy for inverse-electron-demand Diels-Alder reactions: highly efficient in situ substrate generation and activation to construct azaspirocyclic skeletons. , 2012, Angewandte Chemie.

[6]  M. Shi,et al.  Asymmetric substitutions of O-Boc-protected Morita-Baylis-Hillman adducts with pyrrole and indole derivatives. , 2012, Organic & biomolecular chemistry.

[7]  Jun Xu,et al.  Thiourea-Catalyzed Enantioselective Fluorination of β-Keto Esters , 2012 .

[8]  J. Li,et al.  Synthesis of highly functionalized chiral 3,3'-disubstituted oxindoles via an organocatalytic enantioselective Michael addition of nitroalkanes to indolylidenecyanoacetates. , 2012, Organic letters.

[9]  Yixin Lu,et al.  From the Feist-Bénary reaction to organocatalytic domino Michael-alkylation reactions: asymmetric synthesis of 3(2H)-furanones. , 2012, Chemistry.

[10]  C. Barbas,et al.  Core structure-based design of organocatalytic [3+2]-cycloaddition reactions: highly efficient and stereocontrolled syntheses of 3,3'-pyrrolidonyl spirooxindoles. , 2012, Chemistry.

[11]  Natsumi Shimizu,et al.  Catalytic asymmetric synthesis of stable oxetenes via Lewis acid-promoted [2+2] cycloaddition. , 2011, Journal of the American Chemical Society.

[12]  K. Mikami,et al.  Fragment-Based Reaction Discoveryof Non-Ene-Type Carbon-Carbon Bond-Forming Reactions:Catalytic Asymmetric Oxetane Synthesis by Screening OlefinicReactants without Allylic Hydrogen , 2011 .

[13]  Tongen Wang,et al.  DABCO-catalyzed [2+2] cycloaddition reactions of allenoates and trifluoromethylketones: synthesis of 2-alkyleneoxetanes , 2011 .

[14]  Scott J. Miller,et al.  Divergent Reactivity in Amine- and Phosphine-Catalyzed C–C Bond-Forming Reactions of Allenoates with 2,2,2-Trifluoroacetophenones , 2011 .

[15]  M. Shi,et al.  Enantioselective Intermolecular Rauhut-Currier Reaction of Electron-Deficient Allenes with Maleimides , 2011 .

[16]  M. Shi,et al.  Novel Quinidine-Derived Organocatalysts for the Asymmetric Substitutions of O-Boc-Protected Morita–Baylis–Hillman Adducts , 2011 .

[17]  Pan‐Lin Shao,et al.  N-Heterocyclic Carbene-Catalyzed Cyclization of Unsaturated Acyl Chlorides and Ketones , 2011 .

[18]  M. Shi,et al.  Quinidine derived organocatalysts for the nucleophile promoted asymmetric [4+2] cycloaddition reaction of salicyl N-tosylimine with allenic esters , 2011 .

[19]  P. Retailleau,et al.  Cinchona alkaloid amide catalyzed enantioselective formal [2+2] cycloadditions of allenoates and imines: synthesis of 2,4-disubstituted azetidines. , 2011, Angewandte Chemie.

[20]  N. Meanwell.  Synopsis of some recent tactical application of bioisosteres in drug design. , 2011, Journal of medicinal chemistry.

[21]  M. Shi,et al.  Highly Diastereo‐ and Enantioselective Vinylogous Mannich Reactions of Fluorinated Aldimines with Siloxyfurans , 2011 .

[22]  A. Mazzanti,et al.  Organocatalytic Michael-alkylation cascade: the enantioselective nitrocyclopropanation of oxindoles. , 2011, Chemistry.

[23]  Yixin Lu,et al.  Enantioselective Morita-Baylis-Hillman reaction of isatins with acrylates: facile creation of 3-hydroxy-2-oxindoles. , 2011, Organic letters.

[24]  M. Shi,et al.  Construction of chiral quaternary carbon through Morita-Baylis-Hillman reaction: an enantioselective approach to 3-substituted 3-hydroxyoxindole derivatives. , 2010, Chemistry.

[25]  Erick M. Carreira,et al.  Oxetane als vielseitige Bausteine in der Wirkstoff‐Forschung und Synthese , 2010 .

[26]  E. Carreira,et al.  Oxetanes as versatile elements in drug discovery and synthesis. , 2010, Angewandte Chemie.

[27]  M. Shi,et al.  Asymmetric Aza-Morita-Baylis-Hillman Reactions of Alkyl Vinyl Ketones with N-Protected Imines or In Situ Generated N-Protected Imines , 2010 .

[28]  B. Foxman,et al.  Asymmetric vinylogous aldol reaction of silyloxy furans with a chiral organic salt. , 2010, Journal of the American Chemical Society.

[29]  Franz Schuler,et al.  Oxetanes in drug discovery: structural and synthetic insights. , 2010, Journal of medicinal chemistry.

[30]  C. Song,et al.  Cinchona‐Catalyzed Nucleophilic 1,2‐Addition to CO and CN Bonds , 2009 .

[31]  Hyeung‐geun Park,et al.  Cinchona-based phase-transfer catalysts for asymmetric synthesis. , 2009, Chemical communications.

[32]  Jieping Zhu,et al.  Invertible enantioselectivity in 6'-deoxy-6'-acylamino-beta-isocupreidine-catalyzed asymmetric aza-Morita-Baylis-Hillman reaction: key role of achiral additive. , 2009, Organic letters.

[33]  Yixin Lu,et al.  Asymmetric catalysis with chiral primary amine-based organocatalysts. , 2009, Chemical communications.

[34]  M. Shi,et al.  Reactions of monoaryl-substituted methylenecyclobutanes and methylenecyclopropanes with 1-hydroxybenzotriazole (HOBt), 1-hydroxy-7-azabenzotriazole (HOAt), and 1-hydroxysuccinimide (HOSu). , 2009, The Journal of organic chemistry.

[35]  S. Matsunaga,et al.  Catalytic asymmetric synthesis of 2,2-disubstituted oxetanes from ketones by using a one-pot sequential addition of sulfur ylide. , 2009, Angewandte Chemie.

[36]  Yan Liu,et al.  Catalytic asymmetric conjugate addition of simple alkyl thiols to alpha,beta-unsaturated N-acylated oxazolidin-2-ones with bifunctional catalysts. , 2009, Journal of the American Chemical Society.

[37]  Yian Shi,et al.  Organocatalytic oxidation. Asymmetric epoxidation of olefins catalyzed by chiral ketones and iminium salts. , 2008, Chemical reviews.

[38]  E. Carreira,et al.  Spirocyclic oxetanes: synthesis and properties. , 2008, Angewandte Chemie.

[39]  M. Shi,et al.  Asymmetric Morita-Baylis-Hillman reaction of arylaldehydes with 2-cyclohexen-1-one catalyzed by chiral bis(thio)urea and DABCO. , 2008, Organic letters.

[40]  S. Purser,et al.  Fluorine in medicinal chemistry. , 2008, Chemical Society reviews.

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

[42]  M. Shi,et al.  A highly efficient asymmetric Michael addition of anthrone to nitroalkenes with cinchona organocatalysts , 2007 .

[43]  Jieping Zhu,et al.  The enantioselective Morita-Baylis-Hillman reaction and its aza counterpart. , 2007, Angewandte Chemie.

[44]  Géraldine Masson,et al.  Enantioselektive Morita‐Baylis‐Hillman‐Reaktionen und ihre Aza‐Varianten , 2007 .

[45]  J. Campagne,et al.  Synthetic Approaches to α,β-Unsaturated δ-Lactones and Lactols , 2007 .

[46]  E. Carreira,et al.  Oxetanes as promising modules in drug discovery. , 2006, Angewandte Chemie.

[47]  J. V. van Maarseveen,et al.  Cupreines and cupreidines: an emerging class of bifunctional cinchona organocatalysts. , 2006, Angewandte Chemie.

[48]  Tommaso Marcelli,et al.  Cupreine und Cupreidine: eine außergewöhnliche Klasse von bifunktionalen Cinchona‐Organokatalysatoren , 2006 .

[49]  J. Wang,et al.  Highly Efficient Approach to 4‐Ethoxy‐5,6‐dihydro‐6,6‐disubstituted Pyran‐2‐ones using a Combinational Lewis Acid‐Base System , 2006 .

[50]  P. Guiry,et al.  Synthesis of Dihydrofurans Substituted in the 2‐Position , 2005 .

[51]  M. Shi,et al.  Aza-Baylis-Hillman reactions of N-tosylated aldimines with activated allenes and alkynes in the presence of various Lewis base promoters. , 2005, The Journal of organic chemistry.

[52]  J. Campagne,et al.  Catalytic and asymmetric vinylogous mukaiyama reactions on aliphatic ketones: formal asymmetric synthesis of taurospongin a. , 2005, Journal of the American Chemical Society.

[53]  Ming Xian,et al.  Toward understanding how the lactone moiety of discodermolide affects activity. , 2005, Journal of the American Chemical Society.

[54]  Yong Xu,et al.  Catalytic, asymmetric aza-Baylis-Hillman reaction of N-sulfonated imines with activated olefins by quinidine-derived chiral amines. , 2005, Chemistry.

[55]  K. Ding,et al.  Enantioselective catalysis of the hetero-Diels-Alder reaction between Brassard's diene and aldehydes by hydrogen-bonding activation: a one-step synthesis of (S)-(+)-dihydrokawain. , 2004, Chemistry.

[56]  P. Dalko,et al.  In the golden age of organocatalysis. , 2004, Angewandte Chemie.

[57]  Peter I. Dalko,et al.  Im Goldenen Zeitalter der Organokatalyse , 2004 .

[58]  Yian Shi.  Organocatalytic asymmetric epoxidation of olefins by chiral ketones. , 2004, Accounts of chemical research.

[59]  S. Saaby,et al.  Asymmetric construction of quaternary stereocenters by direct organocatalytic amination of α-substituted α-cyanoacetates and β-dicarbonyl compounds , 2004 .

[60]  M. O'donnell,et al.  The enantioselective synthesis of alpha-amino acids by phase-transfer catalysis with achiral Schiff base esters. , 2004, Accounts of chemical research.

[61]  Lili Lin,et al.  Highly enantioselective hetero-Diels-Alder reaction of Brassard diene with aromatic aldehydes. , 2004, Organic letters.

[62]  L. Tang,et al.  Asymmetric organic catalysis with modified cinchona alkaloids. , 2004, Accounts of chemical research.

[63]  K. Jørgensen,et al.  Hetero‐Diels−Alder Reactions of Ketones — A Challenge for Chemists , 2004 .

[64]  K. Jørgensen,et al.  Organocatalytic enantioselective conjugate addition to alkynones. , 2004, Journal of the American Chemical Society.

[65]  M. Shi,et al.  Abnormal aza-Baylis-Hillman reaction of N-tosylated imines with ethyl 2,3-butadienoate and penta-3,4-dien-2-one. , 2003, Organic letters.

[66]  Scott J. Miller,et al.  Nucleophilic chiral amines as catalysts in asymmetric synthesis. , 2003, Chemical reviews.

[67]  D. Basavaiah,et al.  Recent advances in the Baylis-Hillman reaction and applications. , 2003, Chemical reviews.

[68]  Yong Xu,et al.  Catalytic, asymmetric Baylis-Hillman reaction of imines with methyl vinyl ketone and methyl acrylate. , 2002, Angewandte Chemie.

[69]  J. Deisenhofer,et al.  Structural Mechanism for Statin Inhibition of HMG-CoA Reductase , 2001, Science.

[70]  K. A. Jørgensen.  Katalytische asymmetrische Hetero-Diels-Alder-Reaktionen von Carbonylverbindungen und Iminen , 2000 .

[71]  Jørgensen,et al.  Catalytic Asymmetric Hetero-Diels-Alder Reactions of Carbonyl Compounds and Imines. , 2000, Angewandte Chemie.

[72]  D. Young,et al.  Convenient syntheses of [18O]benzyl alcohol and [13C-carboxy, 18O1]Benzoic acid of high isotopic purity , 2000 .

[73]  A. Howell,et al.  An Unanticipated Ring-Opening of 2-Methyleneoxetanes: A Fundamentally New Approach to the Preparation of Homopropargylic Alcohols. , 1998, The Journal of organic chemistry.

[74]  A. Howell,et al.  A 2-methyleneoxetane analog of orlistat demonstrating inhibition of porcine pancreatic lipase. , 1998, Bioorganic & medicinal chemistry letters.

[75]  T. Nakatani,et al.  Total Synthesis of (-)-PA-48153C, a Novel Immunosuppressive 2-Pyranone Derivative , 1995 .

[76]  M. VanNieuwenhze,et al.  Catalytic Asymmetric Dihydroxylation , 1994 .

[77]  J. Wilkinson.  Recent advances in the selective formation of the carbon-fluorine bond , 1992 .

[78]  S. Rozen.  Elemental fluorine as a legitimate reagent for selective fluorination of organic compounds , 1988 .

[79]  Scott R. Wilson,et al.  Rearrangement of unsaturated acylhydroxybenzotriazoles , 1985 .

[80]  A. Endo,et al.  Compactin (ML-236B) and related compounds as potential cholesterol-lowering agents that inhibit HMG-CoA reductase. , 1985, Journal of medicinal chemistry.

[81]  S. Ōmura,et al.  Oxetin, a new antimetabolite from an actinomycete. Fermentation, isolation, structure and biological activity. , 1984, The Journal of antibiotics.

[82]  M. Hamberg,et al.  Thromboxanes: a new group of biologically active compounds derived from prostaglandin endoperoxides. , 1975, Proceedings of the National Academy of Sciences of the United States of America.

[83]  A. McPhail,et al.  Plant antitumor agents. VI. The isolation and structure of taxol, a novel antileukemic and antitumor agent from Taxus brevifolia. , 1971, Journal of the American Chemical Society.

[84]  Tongen Wang,et al.  N‐Heterocyclic Carbene‐Catalyzed [2+2+2] Annulation of Allenoates with Trifluoromethylketones , 2012 .

[85]  K. Soai,et al.  Asymmetric synthesis of 2-aryl substituted oxetanes by enantioselective reduction of β-halogenoketones using lithium borohydride modified with N,N′-dibenzoylcystine , 1986 .