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Development of New Methods for the Synthesis of Aldehydes, Arenes and Trifluoromethylated Compounds

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Development of New Methods for the Synthesis of Aldehydes, Arenes and Trifluoromethylated Compounds Development of New Methods for the Synthesis of Aldehydes, Arenes and Trifluoromethylated Compounds vom Fachbereich Chemie der Technischen Universität Kaiserslautern zur Verleihung des akademischen Grades “Doktor der Naturwissenschaften“ genehmigte Dissertation D 386 Vorgelegt von Bilal Ahmad Khan, MSc geboren in Bagh AJK (Pakistan) Betreuer Prof. Dr. Lukas J. Gooßen Kaiserslautern, 2012 Die vorliegende Arbeit wurde in der Zeit von September 2008 bis March 2012 in der Arbeitsgruppe von Prof. Dr. Lukas J. Gooßen an der Technischen Universität Kaiserslautern angefertigt. Prüfungskommission Vorsitzender: Prof. Dr. Helmut Sitzmann 1. Gutachter: Prof. Dr. Lukas J. Gooßen 2. Gutachter: Prof. Dr. Stefan Kubik Tag der mündlichen Prüfung: 30-03-2012 Acknowledgement First and foremost, I would like to express my sincere gratitude to Prof. Dr. Lukas J. Gooßen for giving me the opportunity to carry out my Ph.D. work under his supervision. Appreciation goes to him for all his contribution of time, ideas, and funding to make my Ph.D. experience productive and stimulating. I am also thankful to Mrs. Gooßen for all the help in finalizing my manuscripts. I would like to thank Prof. Dr. Stefan Kubik and Prof. Dr. Helmut Sitzmann for being in my examination committee. HEC Pakistan and the University of Azad Jammu and Kashmir are gratefully acknowledged for providing me with financial support to complete my Ph. D. I also appreciate Abdul Qayyum Tahir for his timely efforts in the extension of my fellowship. I am grateful to ISGS for all the support during my stay in Kaiserslautern and nominating me for the DAAD fellowship to write my Ph.D. thesis. I am especially thankful to N. Rodríguez, C. Linder, F. Costa, T. Fett, T. Knauber, A. Buba, P. Lange, A. Fromm, M. Blanchot, C. Oppel, D. Ohlmann, K. Salih, P. Mamone, R. Bauer, M. Rudzki, M. Arndt, M. Grünberg, B. Song, S. Bhadra, F. Collet, W. Dzik and S. Baader for providing me with an outstanding experience in and outside labs. Thanks to Dr. N. Rodríguez, F. Costa, T. Fett, Dr. T. Knauber and A. Buba for fruitful discussion during collaborative projects. I am thankful to Dr. T. Knauber for reviewing my thesis. I would like to thank Mrs. Müller and Mr. Kelm from NMR facility, Mrs. Biel, Mrs. Dusch, Mrs. Ellmer and Mrs. Bergsträsse from the analytical department and Mr. Napast, Mr. Rahm, and Mr. Schröer from the chemical storage facility. In the end, I owe my deepest gratitude to my parents and family members. They stood by my side in every aspect of my life. Without their support and encouragement, I would have not earned this degree. Publications Parts of this work have been published in the following journals: • B. A. Khan, A. E. Buba, L. J. Gooßen, Chem. Eur. J . 2012, 18 , 1577-1581: Oxidative Trifluoromethylation of Arylboronates with Shelf-Stable Potassium (trifluoromethyl)trimethoxyborate . • L. J. Gooßen, B. A. Khan, T. Fett, M. Treu, Adv. Synth. Catal . 2010 , 352 , 2166-2170: Low-pressure Hydrogenation of Arenecarboxylic Acids to Aryl Aldehydes . • L. J. Gooßen, F. Manjolinho, B. A. Khan, N. Rodríguez, J. Org. Chem. 2009 , 74 , 2620- 2623: Microwave assisted Cu-catalyzed protodecarboxylation of aromatic carboxylic acids. Abbreviations Ac Acetyl acac Acetylacetonate AcOH Acetic acid Ad. Adamantyl Ar Aryl AS&C Advenced Synthesis and Catalysis BINAP Bis-(diphenylphosphino)-1,1’-binaphthaline Bipy 2,2’-bipyridin Bn Benzyl BOC Di-tert -butylldicarbonate Brett-Phos 2-(Dialkylphosphino)3,6-dimethoxy-2’,4’,6’-triisopropyl-1,1’biphenyl Bz Benzoyl CEJ Chemistry, A European Journal COD 1,5-Cycloctadiene Cy Cyclohexyl dba Dibenzylidene acetone DCE 1,2-Dichloroethane DMA N,N -Dimethylacetamide DMF N,N -Dimethylforamide DMPU N,N -Dimethylpropyleneurea DPE-Phos Bis(2-diphenylphosphino)-ethane Dppp 1,1-Bis(diphenylphosphino)-propane DMSO Dimethylsulfoxide EI Electron Ionization Et Ethyl eq. Equivalent F-acac Hexafluoroacetylacetonate GC Gas chromatography HMPA Hexamethylphosphoramide IPr 1,3-bis(2,6-diisopropyl)-phenyl-imidazol-2-ylidene IR Infrared JOC Journal of Organic Chemistry John-phos 2-(Biphenyl)dialkylphosphine L Ligand M Metal MeCN Acetonitrile Me Methyl Mes Mesityl MS Molecular sieves nBu n-Butyl NHC N-Heterocyclic carbine NMP N-Methyl-2-pyrrolidone nPr n-Propyl Nu Nucleophile PCy 3 Tricyclohexyl phosphine Ph Phenyl Phen. 1,10-Phenanthroline Piv. Pivalic anhydride PivOH Pivalic acid ppm Parts per million RT Room temperature Ru-Phos 2-Dicyclohexylphosphino-2’,6’-di-isopropoxy-1,1’-biphenyl SET Single electron transfer TASF Tris(dimethylaminosulfonium) difluorotrimethylsilicate TBAf Tetrabutylammonium fluoride tBu Tertiary butyl Tf Trifluoromethansulfonyl TFA Trifluoroacetic acid THF Tetrahydrofuran Tol. Toluene X Halide or pseudo halide X-phos 2-(Dicyclohexylphosphino)-2’,4’,6’-isopropylbiphenyl Structure Numbering The chemical structures of each chapter are numbered separately for fast and easy understanding of the reader. The term is composed of a second level chapter number followed by hyphen and a sequential number for each chemical structure. For example, 3.2-1 represents compound one in chapter 3.2. Identical chemical structures in different chapters are represented by different numbers. In the experimental section, chemical structures reported in the publications are represented by the abbreviations of the journal followed by a hyphen and structure number of the molecule, such as AS&C-2a represents the compound 2a in the “Advanced Synthesis and Catalysis” paper. TABLE OF CONTENTS Table of Contents 1 Introduction............................................................................................................................. 1 1.1 Modern Technologies in Fine Chemical Production ...................................................... 1 1.1.1 Catalysis.................................................................................................................. 2 1.1.1.1 Hydrogenation Reactions.................................................................................... 4 1.1.2 Unconventional Process Techniques ...................................................................... 5 1.1.2.1 Microwave-Assisted Synthesis........................................................................... 5 1.1.2.2 Continuous Flow-Through Technology.............................................................. 7 1.2 Carboxylic Acids as Substrates in Catalytic Transformations........................................ 8 1.2.1 Direct Reactions of Carboxylic Acids .................................................................... 9 1.2.1.1 Reactions via Metal Carboxylates ...................................................................... 9 1.2.1.2 Reactions by Extrusion of CO 2 ......................................................................... 11 1.2.2 Reactions of in situ Activated Carboxylic Acids.................................................. 18 1.2.2.1 Reaction via Acyl Metal Species...................................................................... 18 1.2.2.2 Reactions via Decarbonylation ......................................................................... 19 2 Aims of the Research............................................................................................................ 22 3 Synthesis of Aldehydes from Carboxylic Acids................................................................... 23 3.1 State of the Art Aldehyde Synthesis............................................................................. 24 3.1.1 Aldehyde Synthesis via Carbonylation Reactions ................................................ 24 3.1.2 Aldehyde Synthesis via Oxidation Reactions....................................................... 25 3.1.3 Aldehyde Synthesis via Reduction Reactions....................................................... 26 3.2 Direct Reduction of Carboxylic Acids to Aldehydes ................................................... 29 3.2.1 Direct Hydrogenation of Carboxylic Acids to Aldehydes.................................... 30 3.3 Results and Discussions................................................................................................ 31 3.3.1 Low-Pressure Hydrogenation of Arenecarboxylic Acids to Aryl Aldehydes ...... 31 3.4 Summary and Outlook.................................................................................................. 38 4 Synthesis of Arenes from Carboxylic Acids......................................................................... 39 4.1 Protodecarboxylations................................................................................................... 39 4.2 Results and Discussions................................................................................................ 44 4.2.1 Use of Modern Technology for Protodecarboxylations........................................ 44 4.2.2 Microwave-Assisted Cu-Catalyzed Protodecarboxylation of Arenecarboxylic Acids. 44 4.3 Recent Advances in the Protodecarboxylations............................................................ 50 4.4 Outlook ......................................................................................................................... 51 i TABLE OF CONTENTS 5 Synthesis of Trifluoromethylated Compounds..................................................................... 53 5.1 Properties Trifluoromethylated Compounds................................................................. 53 5.2 Trifluoromethylation Reactions.................................................................................... 54 5.2.1 Swarts Reaction:
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