DABCO- and DBU-promoted one-pot reaction of N-sulfonyl ketimines with Morita–Baylis–Hillman carbonates: a sequential approach to (2-hydroxyaryl)nicotinate derivatives

An intriguing DABCO-catalyzed and DBU-promoted one-pot synthesis of an important class of (2-hydroxyaryl)pyridine derivatives bearing a carboxylate or a nitrile group suitably placed at C3 position of the aza-ring has been achieved in acceptable chemical yields with a broad functional group tolerance. This sequential C–C/C–N bond making process proceeds through a regioselective allylic alkylation/aza-Michael reaction between MBH carbonates derived from an acrylate/acrylonitrile and N-sulfonyl ketimines as C,N-binucleophiles catalyzed by DABCO, followed by elimination of SO2 under the influence of base and subsequent aromatization in an open atmosphere.

[1]  S. Samanta,et al.  Microwave-Assisted and Base-Promoted Domino Reaction of Cyclic N-Sulfonyl Ketimines with α,β-Disubstituted Nitroalkenes: A Green Access to 2-Hydroxyarylpyridines , 2018, Asian Journal of Organic Chemistry.

[2]  S. Mobin,et al.  Stereoselective Synthesis of 3,3-Disubstituted Oxindoles and Spirooxindoles via Allylic Alkylation of Morita-Baylis-Hillman Carbonates of Isatins with Cyclic Sulfamidate Imines Catalyzed by DABCO. , 2018, The Journal of organic chemistry.

[3]  Fei Ling,et al.  Copper Catalysis for Nicotinate Synthesis through β‐Alkenylation/Cyclization of Saturated Ketones with β‐Enamino Esters , 2018 .

[4]  S. Samanta,et al.  Metal- and Solvent-Free Approach to Diversely Substituted Picolinates via Domino Reaction of Cyclic Sulfamidate Imines with β,γ-Unsaturated α-Ketocarbonyls. , 2017, The Journal of organic chemistry.

[5]  S. Singh,et al.  Design and synthesis of ruthenium bipyridine catalyst: An approach towards low-cost hydroxylation of arenes and heteroarenes , 2017 .

[6]  W. Tan,et al.  Synthesis of Highly Substituted Pyridines through Copper-Catalyzed Condensation of Oximes and α,β-Unsaturated Imines. , 2017, Angewandte Chemie.

[7]  Hyunwoo Kim,et al.  Water as a Hydroxy Source in a RhIII‐Catalyzed Directed C−H Hydroxylation of 2‐Arylpyridines , 2017 .

[8]  Bing Zhou,et al.  Rhodium(III)-Catalyzed Selective C-H Acetoxylation and Hydroxylation Reactions. , 2017, Organic letters.

[9]  S. Samanta,et al.  A Metal‐Free Based New Approach to 2,4‐Disubstituted Pyridines via One‐Pot Sequential Reaction of Cyclic Sulfamidate Imines with β‐Substituted Acroleins , 2017 .

[10]  S. Mobin,et al.  Domino reaction of cyclic sulfamidate imines with Morita-Baylis-Hillman acetates promoted by DABCO: a metal-free approach to functionalized nicotinic acid derivatives. , 2017, Organic & biomolecular chemistry.

[11]  H. Asahara,et al.  Tailor-made synthesis of fully alkylated/arylated nicotinates by FeCl3-mediated condensation of enamino esters with enones. , 2017, Chemical communications.

[12]  Wei Zhang,et al.  One-Pot Reactions for Modular Synthesis of Polysubstituted and Fused Pyridines. , 2016, Organic letters.

[13]  Prasenjit Das,et al.  Aerobic Direct C(sp2)-H Hydroxylation of 2-Arylpyridines by Palladium Catalysis Induced with Aldehyde Auto-Oxidation , 2016 .

[14]  R. Baxter,et al.  Unprotected Amino Acids as Stable Radical Precursors for Heterocycle C-H Functionalization. , 2016, Organic letters.

[15]  Changfeng Hu,et al.  Metal-Free Synthesis of Fully Substituted Pyridines via Ring Construction Based on the Domino Reactions of Enaminones and Aldehydes. , 2016, The Journal of organic chemistry.

[16]  S. Mobin,et al.  Access to 4,6-Diarylpicolinates via a Domino Reaction of Cyclic Sulfamidate Imines with Morita-Baylis-Hillman Acetates of Nitroolefins/Nitrodienes. , 2016, The Journal of organic chemistry.

[17]  Abraham Thomas,et al.  One-Pot Synthesis of Highly Substituted Nicotinic Acid Derivatives Based on a Formylation Strategy of Enamino Keto Esters. , 2016, The Journal of organic chemistry.

[18]  Xufeng Sun,et al.  Discovery of pyridine-based agrochemicals by using Intermediate Derivatization Methods. , 2016, Bioorganic & medicinal chemistry.

[19]  O. Larionov,et al.  Recent Advances in the C-H-Functionalization of the Distal Positions in Pyridines and Quinolines. , 2015, Tetrahedron.

[20]  Huanfeng Jiang,et al.  Cu-Catalyzed Three-Component Cascade Annulation Reaction: An Entry to Functionalized Pyridines. , 2015, The Journal of organic chemistry.

[21]  D. T. McQuade,et al.  Synthesis and Reactivity Profile of Ylidenemalononitrile Enamines and Their Ester Analogs Towards Electrophiles and Nucleophiles. , 2015, The Journal of organic chemistry.

[22]  Zhi‐Xiang Yu,et al.  Ruthenium-Catalyzed Formal Dehydrative [4 + 2] Cycloaddition of Enamides and Alkynes for the Synthesis of Highly Substituted Pyridines: Reaction Development and Mechanistic Study. , 2015, Journal of the American Chemical Society.

[23]  N. Tada,et al.  Direct ortho‐Hydroxylation of 2‐Phenylpyridines using Palladium(II) Chloride and Hydrogen Peroxide , 2015 .

[24]  J. Ellman,et al.  Facile Rh(III)-Catalyzed Synthesis of Fluorinated Pyridines. , 2015, Organic letters.

[25]  Ping Liu,et al.  Palladium-Catalyzed Aryl C(sp(2))-H Bond Hydroxylation of 2-Arylpyridine Using TBHP as Oxidant. , 2015, The Journal of organic chemistry.

[26]  Ch. Raji Reddy,et al.  Aza-annulation of enynyl azides: a new approach to substituted pyridines. , 2015, Organic letters.

[27]  N. Jiao,et al.  Cu-catalyzed concise synthesis of pyridines and 2-(1H)-pyridones from acetaldehydes and simple nitrogen donors. , 2015, Organic letters.

[28]  Zhi‐Xiang Wang,et al.  N-heterocyclic carbene catalyzed cyclocondensation of α,β-unsaturated carboxylic acids: enantioselective synthesis of pyrrolidinone and dihydropyridinone derivatives. , 2014, Angewandte Chemie.

[29]  Jean-Marie Grassot,et al.  Metal-free multicomponent syntheses of pyridines. , 2014, Chemical reviews.

[30]  Chunhao Yang,et al.  Synthesis of multisubstituted 2-aminopyrroles/pyridines via chemoselective Michael addition/intramolecular cyclization reaction. , 2014, Organic letters.

[31]  Cheol‐Min Park,et al.  Transition-metal-free synthesis of substituted pyridines via ring expansion of 2-allyl-2H-azirines. , 2014, Organic letters.

[32]  Cheol‐Min Park,et al.  A catalyst-controlled selective synthesis of pyridines and pyrroles , 2014 .

[33]  F. Gagosz,et al.  Gold-catalyzed synthesis of functionalized pyridines by using 2H-azirines as synthetic equivalents of alkenyl nitrenes. , 2014, Angewandte Chemie.

[34]  Lin Dong,et al.  Highly functionalized pyridines synthesis from N-sulfonyl ketimines and alkynes using the N-S bond as an internal oxidant. , 2014, Organic letters.

[35]  Sunliang Cui,et al.  Divergent syntheses of 2-aminonicotinonitriles and pyrazolines by copper-catalyzed cyclization of oxime ester. , 2014, Organic letters.

[36]  T. Rovis,et al.  Rh(III)-Catalyzed Decarboxylative Coupling of Acrylic Acids with Unsaturated Oxime Esters: Carboxylic Acids Serve as Traceless Activators , 2014, Journal of the American Chemical Society.

[37]  D. T. McQuade,et al.  Investigating the continuous synthesis of a nicotinonitrile precursor to nevirapine , 2013, Beilstein journal of organic chemistry.

[38]  Marcus Baumann,et al.  An overview of the synthetic routes to the best selling drugs containing 6-membered heterocycles , 2013, Beilstein journal of organic chemistry.

[39]  Hyun Ju Lee,et al.  An Efficient Synthesis of Poly-Substituted Phenols and Pyridines from Morita-Baylis-Hillman Acetates and Diethyl Oxalacetate , 2013 .

[40]  jin-quan yu,et al.  Developing ligands for palladium(II)-catalyzed C-H functionalization: intimate dialogue between ligand and substrate. , 2013, The Journal of organic chemistry.

[41]  J. Iqbal,et al.  IBX mediated reaction of β-enamino esters with allylic alcohols: a one pot metal free domino approach to functionalized pyridines. , 2013, Chemical communications.

[42]  Frédéric Liéby-Muller,et al.  Metal-Free Michael-Addition-Initiated Three-Component Reaction for the Regioselective Synthesis of Highly Functionalized Pyridines: Scope, Mechanistic Investigations and Applications , 2013 .

[43]  Qing‐Zhong Zheng,et al.  PdCl2 and N‐Hydroxyphthalimide Co‐catalyzed C sp 2H Hydroxylation by Dioxygen Activation , 2013 .

[44]  Qing‐Zhong Zheng,et al.  PdCl2 and N-hydroxyphthalimide co-catalyzed C(sp2)-H hydroxylation by dioxygen activation. , 2013, Angewandte Chemie.

[45]  A. Yudin,et al.  Synthesis of multisubstituted pyridines. , 2013, Organic letters.

[46]  R. Takeuchi,et al.  Iridium-catalyzed [2 + 2 + 2] cycloaddition of α,ω-diynes with nitriles. , 2012, Journal of the American Chemical Society.

[47]  J. Ellman,et al.  Synthesis of pyridines from ketoximes and terminal alkynes via C-H bond functionalization. , 2012, The Journal of organic chemistry.

[48]  Xingwei Li,et al.  Rhodium(III)-Catalyzed Synthesis of Pyridines from alpha,beta-Unsaturated Ketoximes and Internal Alkynes , 2011 .

[49]  J. Louie,et al.  A serendipitous discovery: nickel catalyst for the cycloaddition of diynes with unactivated nitriles. , 2011, Angewandte Chemie.

[50]  C. Sumby.  Bridging ligands comprising two or more di-2-pyridylmethyl or amine arms: Alternatives to 2,2′-bipyridyl-containing bridging ligands , 2011 .

[51]  Fan Wu,et al.  A simple and highly efficient iron catalyst for a [2+2+2] cycloaddition to form pyridines. , 2011, Angewandte Chemie.

[52]  Junji Kido,et al.  Multifunctional Materials in High-Performance OLEDs: Challenges for Solid-State Lighting† , 2011 .

[53]  D. Tejedor,et al.  Microwave‐Assisted Diversity‐Oriented Domino Synthesis of Functionalized Nicotinic Acid Derivatives , 2010 .

[54]  B. Heller,et al.  Asymmetric synthesis of axially chiral 1-aryl-5,6,7,8-tetrahydroquinolines by cobalt-catalyzed [2 + 2 + 2] cycloaddition reaction of 1-aryl-1,7-octadiynes and nitriles. , 2010, The Journal of organic chemistry.

[55]  Ken Tanaka,et al.  Rhodium-catalyzed complete regioselective intermolecular cross-cyclotrimerization of aryl ethynyl ethers and nitriles or isocyanates at room temperature. , 2010, Organic letters.

[56]  D. Tejedor,et al.  A convenient domino access to substituted alkyl 1,2-dihydropyridine-3-carboxylates from propargyl enol ethers and primary amines. , 2010, Chemistry.

[57]  C. Allais,et al.  Use of beta,gamma-unsaturated alpha-ketocarbonyls for a totally regioselective oxidative multicomponent synthesis of polyfunctionalized pyridines. , 2009, Chemistry.

[58]  Frédéric Liéby-Muller,et al.  Metal-free Michael addition initiated multicomponent oxidative cyclodehydration route to polysubstituted pyridines from 1,3-dicarbonyls. , 2008, Chemical communications.

[59]  T. Konakahara,et al.  Me3SiCl-promoted three-component coupling reaction of a functionalized enamine, an acetal, and an alkyne: an unprecedented approach to the synthesis of tetrasubstituted pyridines via a [3 + 2 + 1] intermolecular cyclization. , 2008, The Journal of organic chemistry.

[60]  S. Okamoto,et al.  Synthesis of Substituted 2,2′‐Bipyridines and 2,2′:6′,2′′‐Terpyridines by Cobalt‐Catalyzed Cycloaddition Reactions of Nitriles and α,ω‐Diynes with Exclusive Regioselectivity , 2008 .

[61]  M. Bagley,et al.  The Bohlmann-Rahtz Pyridine Synthesis: From Discovery to Applications , 2007 .

[62]  B. Heller,et al.  The fascinating construction of pyridine ring systems by transition metal-catalysed [2 + 2 + 2] cycloaddition reactions. , 2007, Chemical Society reviews.

[63]  Anne-Laure Bonneau,et al.  Unusual sterically controlled regioselective lithiation of 3-bromo-5-(4,4'-dimethyl)oxazolinylpyridine. Straightforward access to highly substituted nicotinic acid derivatives. , 2006, Organic letters.

[64]  Ken Tanaka,et al.  Cationic Rhodium(I)/Modified-BINAP Catalyzed [2+2+2] Cycloaddition of Alkynes with Nitriles , 2006 .

[65]  Yoshihiko Yamamoto,et al.  Ruthenium-catalyzed cycloaddition of 1,6-diynes and nitriles under mild conditions: role of the coordinating group of nitriles. , 2006, Chemistry.

[66]  A. Deiters,et al.  Pyridines via solid-supported [2 + 2 + 2] cyclotrimerization. , 2006, Chemical communications.

[67]  J. Bower,et al.  One-pot multistep Bohlmann-Rahtz heteroannulation reactions: synthesis of dimethyl sulfomycinamate. , 2005, The Journal of organic chemistry.

[68]  P. Langer.  The Asymmetric Baylis‐Hillman‐Reaction , 2004 .

[69]  T. Schubert,et al.  Efficient synthesis of 3-cyano-6-(2-hydroxyphenyl)pyridines by multi-component condensations on beads , 2003 .

[70]  P. Langer,et al.  New Strategies for the Development of an Asymmetric Version of the Baylis-Hillman Reaction This work was supported by the Fonds der Chemischen Industrie (Liebig-scholarship and funds for P. L.). P. L. thanks Prof. Dr. A. de Meijere for his support. , 2000, Angewandte Chemie.

[71]  M. Verma.  Coordination compounds of transition metals , 1984 .

[72]  F. Bohlmann,et al.  Über eine neue Pyridinsynthese , 1957 .

[73]  A. Hantzsch.  Condensationsprodukte aus Aldehydammoniak und ketonartigen Verbindungen , 1881 .