Rhodium(III)-Catalyzed Oxadiazole-Directed Alkenyl C-H Activation for Synthetic Access to 2-Acylamino and 2-Amino Pyridines.

We report herein a Rh(III)-catalyzed alkenyl C-H activation protocol for the coupling of oxadiazoles with alkynes and synthesis of 2-acylamino and 2-amino pyridines, an important heterocyclic scaffold for various naturals products and synthetic pharmaceuticals bearing a readily reacting functional group. The selective protection/deprotection of amino groups through simple solvent switching, good functional group compatibility, superior product yield, and high regioselectivity are some of the notable synthetic features witnessed in this reaction protocol.

[1]  Jin Zhu,et al.  Cobalt(III)-Catalyzed Oxadiazole-Directed C-H Activation for the Synthesis of 1-Aminoisoquinolines. , 2017, Organic letters.

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

[3]  Cheng Yang,et al.  Synthesis of Isocoumarins from Cyclic 2-Diazo-1,3-diketones and Benzoic Acids via Rh(III)-Catalyzed C-H Activation and Esterification. , 2017, The Journal of organic chemistry.

[4]  Jingbo Lan,et al.  Cascade C-H Annulation of Aldoximes with Alkynes Using O2 as the Sole Oxidant: One-Pot Access to Multisubstituted Protoberberine Skeletons. , 2017, Organic letters.

[5]  Xiaolong Yu,et al.  Oxadiazolone-Enabled Synthesis of Primary Azaaromatic Amines. , 2016, Organic letters.

[6]  Baiquan Wang,et al.  Rh(III)-Catalyzed Carbocyclization of 3-(Indolin-1-yl)-3-oxopropanenitriles with Alkynes and Alkenes through C-H Activation. , 2016, Organic letters.

[7]  W. DeGrado,et al.  Exploring N-Arylsulfonyl-l-proline Scaffold as a Platform for Potent and Selective αvβ1 Integrin Inhibitors. , 2016, ACS medicinal chemistry letters.

[8]  Yuanfu Deng,et al.  A [4 + 1] Cyclative Capture Access to Indolizines via Cobalt(III)-Catalyzed Csp(2)-H Bond Functionalization. , 2016, Organic letters.

[9]  Xuan Zhang,et al.  Rhodium-Catalyzed Oxidative Benzannulation of N-Adamantyl-1-naphthylamines with Internal Alkynes via Dual C-H Bond Activation: Synthesis of Substituted Anthracenes. , 2016, Organic letters.

[10]  A. Mobinikhaledi,et al.  Convenient, multicomponent, one-pot synthesis of highly substituted pyridines under solvent-free conditions , 2016 .

[11]  J. Ellman,et al.  Rh(III)-Catalyzed C-H Bond Addition/Amine-Mediated Cyclization of Bis-Michael Acceptors. , 2016, Organic letters.

[12]  Chien‐Hong Cheng,et al.  Cobalt(III)-Catalyzed [5 + 1] Annulation for 2H-Chromenes Synthesis via Vinylic C–H Activation and Intramolecular Nucleophilic Addition , 2016 .

[13]  Dinesh Kumar,et al.  Merging C–H Bond Functionalization with Amide Alcoholysis: En Route to 2-Aminopyridines , 2016 .

[14]  N. Jiao,et al.  Rh- and Cu-Cocatalyzed Aerobic Oxidative Approach to Quinazolines via [4 + 2] C-H Annulation with Alkyl Azides. , 2016, Organic letters.

[15]  Jian Song,et al.  A New Rhodium/Copper-Cocatalyzed C–H Oxidation for the Preparation of Isoquinolin-1-ones , 2016, Synthesis.

[16]  L. Ackermann,et al.  Selective Synthesis of Indoles by Cobalt(III)-Catalyzed C–H/N–O Functionalization with Nitrones , 2016 .

[17]  S. Maddila,et al.  Reusable Ce-V Loaded Alumina Catalyst for Multicomponent Synthesis of Substituted Pyridines in Green Media , 2016 .

[18]  Ying‐Chun Chen,et al.  Spirocyclic Sultam and Heterobiaryl Synthesis through Rh-Catalyzed Cross-Dehydrogenative Coupling of N-Sulfonyl Ketimines and Thiophenes or Furans. , 2016, Organic letters.

[19]  L. Ackermann,et al.  Cobalt-Catalyzed C―H Activation , 2016 .

[20]  G. Allmaier,et al.  2,6-Diamination of substituted pyridines via heterogeneous Chichibabin reaction , 2016 .

[21]  Chunfang Jiang,et al.  Cp*Co(III)-Catalyzed Annulations of 2-Alkenylphenols with CO: Mild Access to Coumarin Derivatives. , 2015, Organic letters.

[22]  P. Maiti,et al.  First report of multiple metal ions containing glass–ceramic material as a heterogeneous ditopic catalyst for the chromatography free synthesis of 2-amino-3,5-dicarbonitrile-6-arylthio-pyridines in water , 2015 .

[23]  Yuhong Zhang,et al.  Transition metal-catalyzed C–H bond functionalizations by the use of diverse directing groups , 2015 .

[24]  D. Kong,et al.  Highly Efficient Rh-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated Nitriles. , 2015, Journal of the American Chemical Society.

[25]  Qi Zhang,et al.  Synthesis, optical properties of multi donor–acceptor substituted AIE pyridine derivatives dyes and application for Au3+ detection in aqueous solution , 2015 .

[26]  D. Stalke,et al.  Ruthenium(II)-catalyzed C-H activation/alkyne annulation by weak coordination with O2 as the sole oxidant. , 2015, Angewandte Chemie.

[27]  Lei Yang,et al.  Transition-metal-catalyzed direct addition of unactivated C-H bonds to polar unsaturated bonds. , 2015, Chemical reviews.

[28]  Z. Zuo,et al.  Ru(II)-catalyzed oxidative spiroannulation of 2-arylphenols with alkynes via a C-H activation/dearomatization strategy. , 2015, The Journal of organic chemistry.

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

[30]  Yingwei Zhao,et al.  Palladium‐Catalyzed Intramolecular Oxidative CH Sulfuration of Aryl Thiocarbamates , 2014 .

[31]  A. Borah,et al.  Recent Advances in Catalytic Functionalization of N‐Oxide Compounds via CH Bond Activation , 2014 .

[32]  N. Jiao,et al.  Recent advances in transition-metal-catalyzed functionalization of unstrained carbon-carbon bonds. , 2014, Chemical reviews.

[33]  S. Banskota,et al.  Synthesis and antiangiogenic activity of 6-amido-2,4,5-trimethylpyridin-3-ols. , 2014, Bioorganic & medicinal chemistry letters.

[34]  Zhangjie Shi,et al.  Transition metal-catalyzed direct nucleophilic addition of C–H bonds to carbon–heteroatom double bonds , 2014 .

[35]  Jung-Ae Kim,et al.  6-Amino-2,4,5-trimethylpyridin-3-ols: a new general synthetic route and antiangiogenic activity. , 2014, European journal of medicinal chemistry.

[36]  Guangtao Li,et al.  Palladium‐Catalyzed CF Bond Formation via Directed CH Activation , 2014 .

[37]  L. Ackermann,et al.  Weakly Coordinating Directing Groups for Ruthenium(II)‐ Catalyzed CH Activation , 2014 .

[38]  Srinivasarao Allu,et al.  Ruthenium-catalyzed synthesis of isoquinolones with 8-aminoquinoline as a bidentate directing group in C-H functionalization. , 2014, The Journal of organic chemistry.

[39]  M. Kanai,et al.  Pyrroloindolone synthesis via a Cp*Co(III)-catalyzed redox-neutral directed C-H alkenylation/annulation sequence. , 2014, Journal of the American Chemical Society.

[40]  N. Cosford,et al.  2-Aminopyridines via reaction of pyridine N-oxides and activated isocyanides. , 2014, The Journal of organic chemistry.

[41]  Tun-Cheng Chien,et al.  Practical synthesis of N-substituted cyanamides via Tiemann rearrangement of amidoximes. , 2014, Organic letters.

[42]  T. R. Johnson,et al.  Prediction of Crizotinib-Midazolam Interaction Using the Simcyp Population-Based Simulator: Comparison of CYP3A Time-Dependent Inhibition between Human Liver Microsomes versus Hepatocytes , 2013, Drug Metabolism and Disposition.

[43]  Jin Zhu,et al.  Rhodium(III)-catalyzed N-nitroso-directed C-H olefination of arenes. High-yield, versatile coupling under mild conditions. , 2013, Journal of the American Chemical Society.

[44]  G. Heinrich,et al.  A new versatile synthesis of 4-substituted diaminopyridine derivatives , 2012 .

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

[46]  Xingwei Li,et al.  Synthesis of quinolines via Rh(III)-catalyzed oxidative annulation of pyridines. , 2011, The Journal of organic chemistry.

[47]  L. Ackermann.  Carboxylate-assisted transition-metal-catalyzed C-H bond functionalizations: mechanism and scope. , 2011, Chemical reviews.

[48]  N. Porter,et al.  New synthetic route to N-tocopherol derivatives: synthesis of pyrrolopyridinol analogue of α-tocopherol from pyridoxine. , 2011, Organic & biomolecular chemistry.

[49]  Liuqing Wei,et al.  General and mild preparation of 2-aminopyridines. , 2010, Organic letters.

[50]  T. Rovis,et al.  Rhodium-catalyzed oxidative cycloaddition of benzamides and alkynes via C-H/N-H activation. , 2010, Journal of the American Chemical Society.

[51]  T. Mei,et al.  Pd(II)-catalyzed amination of C-H bonds using single-electron or two-electron oxidants. , 2009, Journal of the American Chemical Society.

[52]  W. Brennessel,et al.  C−H Activation of Phenyl Imines and 2-Phenylpyridines with [Cp*MCl2]2 (M = Ir, Rh): Regioselectivity, Kinetics, and Mechanism , 2009 .

[53]  Jiang Cheng,et al.  Rhodium–copper–TBAF-catalyzed hydroarylation of alkynes with aryl Trimethoxysilanes , 2009 .

[54]  A. Turpie,et al.  New oral anticoagulants in atrial fibrillation. , 2007, European heart journal.

[55]  I. Davies,et al.  A general and efficient 2-amination of pyridines and quinolines. , 2007, The Journal of organic chemistry.

[56]  A. Fiksdahl,et al.  Nitropyridyl isocyanates in 1,3-dipolar cycloaddition reactions , 2007 .

[57]  S. Croft,et al.  Antikinetoplastid activity of 3-aryl-5-thiocyanatomethyl-1,2,4-oxadiazoles. , 2004, Bioorganic & medicinal chemistry.

[58]  M. Palucki,et al.  A highly efficient synthesis of 2-[3-aminopropyl]-5,6,7,8-tetrahydronaphthyridine via a double Suzuki reaction and a Chichibabin cyclization , 2001 .

[59]  J. Gajewski,et al.  Secondary Deuterium Kinetic Isotope Effects in Irreversible Additions of Hydride and Carbon Nucleophiles to Aldehydes: A Spectrum of Transition States from Complete Bond Formation to Single Electron Transfer , 1999 .