Chemistry of Pyrroles
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CHEMISTRY OF PYRROLES CHEMISTRY OF PYRROLES Boris A. Trofimov Al’bina I. Mikhaleva Elena Yu Schmidt Lyubov N. Sobenina Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2015 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Version Date: 20140815 International Standard Book Number-13: 978-1-4822-3243-1 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. 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Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Contents Preface.......................................................................................................................ix Introduction ...............................................................................................................xi Chapter 1 Synthesis of Pyrroles and N-Vinylpyrroles by the Reaction of Ketones (Ketoximes) with Acetylenes .................................................1 1.1 Heterocyclization of Ketoximes with Acetylene .......................1 1.1.1 Superbase System Alkali Metal Hydroxide–Dimethyl Sulfoxide as the Reaction Catalyst ..........................................................2 1.1.2 Effects of Base Nature and Concentration ...................6 1.1.3 Effect of Solvent ...........................................................9 1.1.4 Effect of Pressure ....................................................... 11 1.1.5 One-Pot Synthesis of Pyrroles from Ketones, Hydroxylamine, and Acetylene ..................................12 1.1.6 Effect of Ketoximes Structure on Yields and Ratio of Pyrroles ........................................................ 16 1.1.6.1 Dialkyl- and Alkylcycloalkylketoximes ..... 16 1.1.6.2 Oximes of Cyclic and Heterocyclic Ketones ....................................................... 16 1.1.6.3 Oximes of Terpenoid Ketones and Their Analogs ............................................. 47 1.1.6.4 Oximes of Ketosteroids .............................. 51 1.1.6.5 Oximes of Alkyl Aryl Ketones ...................54 1.1.6.6 Oximes of Alkyl Hetaryl Pyrroles..............58 1.1.6.7 Functionally Substituted Ketoximes ...........64 1.1.6.8 Oximes of Diketones: Synthesis of Dipyrroles ...................................................66 1.1.6.9 Dioximes of 1,2-Diketones .........................67 1.1.6.10 Dioximes of 1,3-Diketones .........................68 1.1.6.11 Dioximes of 1,4-Diketones ......................... 71 1.1.6.12 Dioximes Separated by Conjugated Systems .......................................................72 1.2 Regiospecificity of the Reaction ..............................................77 1.3 Substituted Acetylenes in the Reaction with Ketoximes .........82 1.3.1 Methylacetylene .........................................................82 1.3.2 Phenylacetylene ..........................................................84 1.3.3 Acylacetylenes ............................................................84 1.3.4 Other Acetylenes ........................................................87 1.4 Vinyl Halides and Dihaloethanes as Synthetic Equivalents of Acetylene .........................................................90 v vi Contents 1.5 Intermediate Stages and Side Reactions ..................................92 1.5.1 Formation of O-Vinyl Oximes ...................................92 1.5.2 Formation of 4H-2-Hydroxy-2,3-Dihydropyrroles ...... 101 1.5.3 Formation of 3H-Pyrroles ........................................ 102 1.5.4 Formation of Pyridines............................................. 103 1.5.5 Formation of Acetylenic Alcohols ........................... 107 1.5.6 Side Products Formed in Trace Amounts ................ 107 1.6 δ-Carbolines from 3-Acylindoles and Acetylene .................. 113 1.7 Reaction of Ketoximes with Acetylene in the Presence of Ketones: One-Pot Assembly of 4-Methylene-3-oxa-1- azabicyclo[3.1.0]hexanes ........................................................ 115 1.8 Transformations of Aldoximes in the Systems MOH/DMSO and MOH/DMSO/Acetylene .......................... 116 1.9 Mechanism of Pyrrole Synthesis from Ketoximes and Acetylene ...................................................... 119 1.9.1 Oximes as Nucleophiles in the Reaction with Acetylenes: Literature Analysis ............................... 119 1.9.2 Possible Mechanisms of Pyrrole Synthesis from Ketoximes and Acetylene ......................................... 123 Chapter 2 Novel Aspects of NH- and N-Vinylpyrroles Reactivity ................... 129 2.1 Reactions with Participation of the Pyrrole Ring .................. 129 2.1.1 Protonation ............................................................... 129 2.1.1.1 Electron Structure of N-Vinylpyrrolium Ions............................................................ 129 2.1.1.2 Dimerization of Protonated N-Vinylpyrroles ........................................ 130 2.1.1.3 Peculiarities of N-Vinylpyrroles Protonation with Hydrogen Halides ......... 131 2.1.1.4 Addition of Hydrogen Halides to the Pyrrole Ring ............................................. 132 2.1.1.5 Protonation of N-Vinylpyrroles with Superacids ................................................. 132 2.1.1.6 Protonation of Hetarylpyrroles ................. 135 2.1.2 Hydrogenation and Dehydrogenation ....................... 137 2.1.2.1 Hydrogenation ........................................... 137 2.1.2.2 Selective Dehydrogenation of 4,5,6,7-Tetrahydroindole ........................... 139 2.1.2.3 Dehydrogenation of 4,5-dihydrobenz[g]indole ......................... 139 2.1.3 Reactions with Electrophilic Alkenes ...................... 142 2.1.3.1 Nucleophilic Addition to Vinyl Sulfones ......................................... 142 2.1.3.2 Reactions with Tetracyanoethylene .......... 145 2.1.4 Reactions with Acetylene ......................................... 154 Contents vii 2.1.4.1 N-Vinylation .............................................. 154 2.1.4.2 Reactions with Electrophilic Acetylenes ..... 157 2.1.4.3 Reactions with 1-Alkylthio-2- chloroacetylenes........................................ 167 2.1.5 Cross-Coupling of Pyrroles with Haloacetylenes.................................................. 168 2.1.5.1 Ethynylation of Pyrroles ........................... 168 2.1.5.2 Reaction of 2-Ethynylpyrroles with 2,3-Dichloro-5,6-dicyano-1,4- benzoquinone ............................................ 182 2.1.5.3 Hydroamination of 2-Ethynylpyrroles ...... 190 2.1.6 Reactions with Carbon Disulfide ............................. 193 2.1.6.1 Synthesis of Pyrrolecarbodithioates ......... 193 2.1.6.2 Addition of Pyrrolecarbodithioate Anions to the Multiple Bond ....................202 2.1.6.3 Reactions of S-Alkylpyrrolecarbodithioates .................205 2.1.6.4 Synthesis of Pyrrolothiazolidines .............206 2.1.6.5 Synthesis of Pyrrolizin-3-One ..................206 2.1.6.6 Reactions of Functionally Substituted C-Vinylpyrroles with Hydroxide Anion: Synthesis of Stable Enols .............. 214 2.1.6.7 Reactions of Functionalized 2-Vinylpyrroles with Amines ...................224 2.1.6.8 Synthesis of 5-Amino-3-(pyrrol-2-yl) pyrazoles ...................................................227 2.1.6.9 Synthesis of 5(3)-Amino-3(5)-(pyrrol- 2-yl)isoxazoles ..........................................236 2.1.7 Alkylation of Pyrroles with Functional Organic Halides ........................................................242 2.1.7.1 Alkylation of Pyrroles with Allyl Halides ............................................242 2.1.7.2 Alkylation of Pyrroles with Propargyl Halides .....................................243 2.1.7.3 Allenylation of Pyrroles with 2,3-Dichloro-1-propene ............................243 2.1.7.4 Allenylation of Pyrroles with 1,2,3-Trichloropropane .............................246