Metal- and Solvent-Free Approach to Diversely Substituted Picolinates via Domino Reaction of Cyclic Sulfamidate Imines with β,γ-Unsaturated α-Ketocarbonyls.

An efficient, solvent-free, and eco-friendly domino reaction of 5/6-membered cyclic sulfamidate imines with a variety of β,γ-unsaturated α-ketocarbonyls in neat conditions under MW irradiation promoted by DABCO as a solid organobase has been developed for the rapid construction of a novel class of densely functionalized picolinates. This interesting metal-solvent-free tactic allows a wide range of useful functionalities on the aryl rings and delivers good to excellent yields of the aforesaid aza-heterocycles within short time spans (20-40 min). A biologically promising imidazo[1,2-a]pyridine was successfully synthesized through our unique procedure.

[1]  Dong Zhang,et al.  Efficient synthesis of multisubstituted 2-alkenylpyridines via 2,3-rearrangement of O-homoallenylic oximes , 2017 .

[2]  Qi Wang,et al.  Associative Covalent Relay: An Oxadiazolone Strategy for Rhodium(III)-Catalyzed Synthesis of Primary Pyridinylamines. , 2017, Angewandte Chemie.

[3]  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 .

[4]  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.

[5]  S. Jana,et al.  (Diacetoxy)iodobenzene-Mediated Oxidative C-H Amination of Imidazopyridines at Ambient Temperature. , 2017, The Journal of organic chemistry.

[6]  Pengfei Sun,et al.  Copper-Catalyzed Selenylation of Imidazo[1,2-a]pyridines with Selenium Powder via a Radical Pathway. , 2017, The Journal of organic chemistry.

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

[8]  P. T. Bremer,et al.  Picolinic acids as β-exosite inhibitors of botulinum neurotoxin A light chain. , 2016, Chemical communications.

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

[10]  T. D. Stack,et al.  Manganese(II)/Picolinic Acid Catalyst System for Epoxidation of Olefins. , 2016, Organic letters.

[11]  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.

[12]  Z. Deng,et al.  Transformation of Streptonigrin to Streptonigrone: Flavin Reductase-Mediated Flavin-Catalyzed Concomitant Oxidative Decarboxylation of Picolinic Acid Derivatives , 2016 .

[13]  I. D. de Esch,et al.  4,6-Diphenylpyridines as Promising Novel Anti-Influenza Agents Targeting the PA-PB1 Protein-Protein Interaction: Structure-Activity Relationships Exploration with the Aid of Molecular Modeling. , 2016, Journal of medicinal chemistry.

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

[15]  H. Zhai,et al.  Synthesis of Polysubstituted Pyridines via a One-Pot Metal-Free Strategy. , 2015, Organic letters.

[16]  E. R. Jarvo,et al.  Silver-Catalyzed Enantioselective Propargylation Reactions of N-Sulfonylketimines , 2015, Organic letters.

[17]  Raquel P. Herrera,et al.  Thiourea‐Catalyzed Addition of Indoles to Aliphatic β,γ‐Unsaturated α‐Ketoesters , 2015 .

[18]  Yuping Dong,et al.  Novel Carbazol-Pyridine-Carbonitrile Derivative as Excellent Blue Thermally Activated Delayed Fluorescence Emitter for Highly Efficient Organic Light-Emitting Devices. , 2015, ACS applied materials & interfaces.

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

[20]  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.

[21]  S. Samanta,et al.  A catalyst-free, efficient green MCR protocol for access to functionalized γ-carbolines in water , 2015 .

[22]  Peter L. Johnson,et al.  Synthesis of Novel Fluoropicolinate Herbicides by Cascade Cyclization of Fluoroalkyl Alkynylimines. , 2015, Organic Letters.

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

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

[25]  S. Santra,et al.  Synthesis of imidazo[1,2-a]pyridines: a decade update. , 2015, Chemical communications.

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

[27]  T. Rovis,et al.  Pyridine synthesis by [4 + 2] cycloadditions of 1-azadienes: hetero-Diels Alder and transition metal-catalysed approaches , 2014 .

[28]  S. Chiba,et al.  Formal [4+2]-annulation of vinyl azides with N-unsaturated aldimines. , 2014, Chemistry, an Asian journal.

[29]  S. Mobin,et al.  An expedient one-pot sequential three-component reaction for the stereoselective synthesis of functionalized spiro-sulfamidate imine fused δ-lactone scaffold , 2014 .

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

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

[32]  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.

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

[34]  A. Hashmi,et al.  Gold(I)-catalyzed diastereoselective hydroacylation of terminal alkynes with glyoxals. , 2014, Angewandte Chemie.

[35]  David B. Baker,et al.  Total Synthesis of the Antitumor Antibiotic (±)-Streptonigrin: First- and Second-Generation Routes for de Novo Pyridine Formation Using Ring-Closing Metathesis , 2013, The Journal of organic chemistry.

[36]  E. Suresh,et al.  N-Heterocyclic carbene catalyzed reaction of cinnamils leading to the formation of 2,3,8-triaryl vinyl fulvenes: an uncommon transformation. , 2013, Organic letters.

[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]  S. Mobin,et al.  L-proline catalyzed stereoselective synthesis of (E)-methyl-α-indol-2-yl-β-aryl/alkyl acrylates: easy access to substituted carbazoles, γ-carbolines and prenostodione. , 2013, Organic & biomolecular chemistry.

[41]  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.

[42]  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.

[43]  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 .

[44]  S. Mobin,et al.  L-Proline catalyzed highly efficient synthesis of Z-5-alkylidene cyclic sulfamidate imines: an easy access to 5-alkyl-substituted cyclic sulfamidate imines , 2013 .

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

[46]  T. Rovis,et al.  Rh(III)-catalyzed regioselective synthesis of pyridines from alkenes and α,β-unsaturated oxime esters. , 2013, Journal of the American Chemical Society.

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

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

[49]  Hao Yan,et al.  Cu(I)-catalyzed synthesis of imidazo[1,2-a]pyridines from aminopyridines and nitroolefins using air as the oxidant. , 2012, The Journal of organic chemistry.

[50]  François Couty,et al.  Increasing the reactivity of nitrogen catalysts. , 2011, Chemistry.

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

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

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

[54]  K. Hong,et al.  Cytotoxic bipyridines from the marine-derived actinomycete Actinoalloteichus cyanogriseus WH1-2216-6. , 2011, Journal of natural products.

[55]  S. Chiba,et al.  Synthesis of azaheterocycles from aryl ketone O-acetyl oximes and internal alkynes by Cu-Rh bimetallic relay catalysts. , 2011, The Journal of organic chemistry.

[56]  Liduo Wang,et al.  A Pyridine‐Containing Anthracene Derivative with High Electron and Hole Mobilities for Highly Efficient and Stable Fluorescent Organic Light‐Emitting Diodes , 2011 .

[57]  Allan M Jordan,et al.  The medicinal chemist's toolbox: an analysis of reactions used in the pursuit of drug candidates. , 2011, Journal of medicinal chemistry.

[58]  A. Jia,et al.  Synthesis of Isoquinolines via Rhodium(III)-Catalyzed Dehydrative C-C and C-N Coupling between Oximines and Alkynes , 2011 .

[59]  P. Sadler,et al.  Organometallic half-sandwich iridium anticancer complexes. , 2011, Journal of medicinal chemistry.

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

[61]  Louis C. Morrill,et al.  Organocatalytic functionalization of carboxylic acids: isothiourea-catalyzed asymmetric intra- and intermolecular Michael addition--lactonizations. , 2011, Journal of the American Chemical Society.

[62]  M. D. Hill,et al.  Recent strategies for the synthesis of pyridine derivatives. , 2010, Chemistry.

[63]  Soyeong Kang,et al.  Enantioselective synthesis of cyclic sulfamidates by using chiral rhodium-catalyzed asymmetric transfer hydrogenation. , 2010, Organic letters.

[64]  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.

[65]  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.

[66]  G. Newkome,et al.  Unexpected isolation of a pentameric metallomacrocycle from the Fe(II)-mediated complexation of 120 degrees juxtaposed 2,2':6',2''-terpyridine ligands. , 2010, Chemistry.

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

[68]  Yanguang Wang,et al.  A cascade approach to pyridines from 2-azido-2,4-dienoates and alpha-diazocarbonyl compounds. , 2009, The Journal of organic chemistry.

[69]  K. Shibatomi,et al.  Development of a New ChiralSpiro Oxazolinylpyridine Ligand (Spymox) for AsymmetricCatalysis , 2009 .

[70]  O. Daugulis,et al.  A general method for copper-catalyzed arylation of arene C-H bonds. , 2008, Journal of the American Chemical Society.

[71]  J. Ellman,et al.  Rh(I)-catalyzed direct arylation of pyridines and quinolines. , 2008, Journal of the American Chemical Society.

[72]  A. Blake,et al.  Interaction of N-(aryl)picolinamides with iridium. N-H and C-H bond activations , 2008 .

[73]  Zhaoguo Zhang,et al.  Highly enantioselective sequential hydrogenation of ethyl 2-oxo-4-arylbut-3-enoate to ethyl 2-hydroxy-4-arylbutyrate. , 2008, The Journal of organic chemistry.

[74]  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.

[75]  S. Buchwald,et al.  A general and efficient method for the Suzuki-Miyaura coupling of 2-pyridyl nucleophiles. , 2008, Angewandte Chemie.

[76]  Yong‐Gui Zhou,et al.  Enantioselective synthesis of cyclic sulfamidates via Pd-catalyzed hydrogenation. , 2008, Organic letters.

[77]  Anne W. Schmidt,et al.  Synthesis and SAR of 2-aryloxy-4-alkoxy-pyridines as potent orally active corticotropin-releasing factor 1 receptor antagonists. , 2008, Journal of medicinal chemistry.

[78]  K. Parthasarathy,et al.  Rhodium-Catalyzed One-Pot Synthesis of Substituted Pyridine Derivatives from α,β-Unsaturated Ketoximes and Alkynes , 2008 .

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

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

[81]  H. Arndt,et al.  Hetero Diels-Alder synthesis of 3-hydroxypyridines: access to the nosiheptide core. , 2007, The Journal of organic chemistry.

[82]  J. S. Carey,et al.  Analysis of the reactions used for the preparation of drug candidate molecules. , 2006, Organic & biomolecular chemistry.

[83]  R. Tanaka,et al.  One-pot synthesis of metalated pyridines from two acetylenes, a nitrile, and a titanium(II) alkoxide. , 2005, Journal of the American Chemical Society.

[84]  L. Markova,et al.  Reactions of 1,5-Diketones with Ammonia and Its Derivatives. (Review) , 2003 .

[85]  B. Druker,et al.  Specific Targeted Therapy of Chronic Myelogenous Leukemia with Imatinib , 2003, Pharmacological Reviews.

[86]  U. Lüning,et al.  Basicity and Solvatochromism of Concave Pyridines with Extended π‐Systems in Protic and Nonprotic Solvents , 2003 .

[87]  J. Bower,et al.  A new one-pot three-component condensation reaction for the synthesis of 2,3,4,6-tetrasubstituted pyridines. , 2002, Chemical communications.

[88]  H. Sakurai,et al.  Ternary complex formation between VO(IV)-picolinic acid or VO(IV)-6-methylpicolinic acid and small blood serum bioligands. , 2000, Journal of inorganic biochemistry.

[89]  G. Duburs,et al.  Synthesis of 1,4-dihydropyridines by cyclocondensation reactions , 1988 .

[90]  R. Ramsay,et al.  Inhibition of mitochondrial NADH dehydrogenase by pyridine derivatives and its possible relation to experimental and idiopathic parkinsonism. , 1986, Biochemical and biophysical research communications.

[91]  M. Kawamura,et al.  Highly selective inhibitors of thromboxane synthetase. 2. Pyridine derivatives. , 1981, Journal of medicinal chemistry.

[92]  C. Redemann,et al.  A Picolinic Acid Derivative: A Plant Growth Regulator , 1963, Science.

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

[94]  N. Ikekawa,et al.  Notes - Reaction Between Acrolein and Ethyl β-Aminocrotonate , 1956 .

[95]  E. Eliel,et al.  Abnormal Chichibabin Reactions. The Condensation of Phenylacetaldehyde and Homoveratric Aldehyde with Ammonia1 , 1953 .

[96]  Reuben G. Jones,et al.  Pyridine Syntheses. II. A New Pyridine Synthesis Leading to Vitamin B6 , 1951 .

[97]  R. C. Elderfield,et al.  STUDIES IN THE PYRIDINE SERIES. II. SYNTHESIS OF 2-METHYL-3-(β-HYDROXYETHYL)PYRIDINE AND OF THE PYRIDINE ANALOG OF THIAMINE (VITAMIN B1) , 1941 .

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