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Synthetic Studies on Balanol, Angucyclines and Catalytic Organic Transformations

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Synthetic Studies on Balanol, Angucyclines and Catalytic Organic Transformations SYNTHETIC STUDIES ON BALANOL, ANGUCYCLINES AND CATALYTIC ORGANIC TRANSFORMATIONS A THESIS SUBMITTED TO THE UNIVERSITY OF PUNE FOR THE DEGREE OF DOCTOR OF PHILOSOPHY (IN CHEMISTRY) BY MAHESH L. PATIL DIVISION OF ORGANIC CHEMISTRY: TECHNOLOGY NATIONAL CHEMICAL LABORATORY PUNE-411 008 INDIA MAY 2001 DEDICATED TO MY BELOVED PARENTS NATIONAL CHEMICAL LABORATORY Dr. Homi Bhabha Road, PUNE-411 008 INDIA Dr. V.H. Deshpande Scientist Organic Chemistry : Technology Division Tel: 020-5893614 CERTIFICATE Certified that the work incorporated in the thesis entitled "Synthetic Studies on Balanol, Angucyclines and Catalytic Organic Transformations" by Mr. Mahesh L. Patil was carried out by the candidate under my supervision. Such material as had been obtained from other sources has been duly acknowledged in the thesis. MAY 2001 (V. H. DESHPANDE) RESEARCH GUIDE ACKNOWLEDGEMENTS With the reverence and zealous pride, 1 take this pleasant opportunity to express my deep sense of gratitude to my research supervisor Dr. V. H. Deshpande, Deputy Director, Division of Organic Chemistry: Technology, National Chemical Laboratory, Pune, for his expert and inspiring guidance, keen interest and commitment to my work and helpful hints throughout my thesis work. It gives me great pleasure in acknowledging my deep sense of gratitude and indebtedness to Dr. H. B. Borate, Scientist, Division of Organic Chemistry: Technology, National Chemical Laboratory, Pune, for his keen interest, valuable suggestions, never diminishing encouragement and for his morale boosting support for this creation. I wish to take this opportunity to thank Dr. T. Ravindranathan for the help and support during my initial period in NCL. I am also thankful to Dr. M. K Gurjar, Head, Division of Organic chemistry: Tech., NCL, Pune, Dr. (Mrs.) R. D. Wakharkar, Dr. S. P. Chavan, Dr. (Mrs.) Bhanu Chanda, Dr. S. K Kamat, Dr. R. A. Joshi, Dr. (Mrs.) R. R. Joshi, Mrs. Latashivdasan, Mrs. Kamalambalkrishnan, Mr. Shivkumar, Dr. R. J. Lahoti for their help in various ways which made my work easygoing. I am very happy to convey my heart felt gratitude and thanks to Dr. U. R. Kalkote, Dr. B. M. Bhawal, Dr. M. K Dongre and Dr. P. P. Wadgoankar for the suggestions and help. I also wish to thank all my friends Ramalingam, Datta Ponde, Janeshwara, Vivek Bulbule, Sabde, Manoj Gote, Nadim, Vishal, Shinde, Shrinivas Hothead, Kishore, Sylesh, Kharul, Amar, Sharma, Sambhaji Chavan, Pashupati, Kale, Gajare, Bar hate, R. R. Deshmukh, C. Ramesh, Varsha, Pallavi, Savita, Jota, Sonali, Swapnaja, Kakde for the cooperation and encouragement. I am very much thankful to the IR, NMR, Mass and Micro analytical groups of NCL. I would not miss this opportunity to express my deep gratitude to my parents, my brother Yogesh Patil, my sister Bhagyashree Deshpande because of whose support, encouragement and sacrifice this piece of work is completed. I also wish to thank my wife Anagha for her encouragement, support and sustained patience during my research work I take opportunity to thank Mr. S. t. Kulkarni, Mr. Uday Kulkarni and Thigale family for morale support. Financial support from CSIR in the form of Senior Research Fellowship is gratefully acknowledged. Finally, I wish to thank the Director, National Chemical Laboratory, Pune, for his permission to submit this research work in the form of Ph. D. thesis. MAY 2001 National Chemical Laboratory, Pune 411 008, India. (Mahesh L. Patil) CONTENTS Page No. General Remarks I Abbreviations II Thesis Abstract III CHAPTER I:SYNTHETIC STUDIES ON ANGUCYCLINE ANTIBIOTICS 1-96 General Introduction 1-12 SECTION A: SYNTHESIS OF (+-)-BRASILIQUINONE B 1.1.0 Introduction 13 1.1.1 Present work 14 1.1.4 Conclusion 24 1.1.5 Experimental 25 SECTION B: ATTEMPTED SYNTHESIS OF BRASILIQUINONE C AND SYNTHESIS OF (+-)-8-DEOXYBRASILIQUINONE B PART I: ATTEMPTED SYNTHESIS OF BRASILIQUINONE C 1.2.0 Introduction 45 1.2.1 Present work 46 PART II: SYNTHESIS OF (+-)-8-DEOXYBRASILIAUINONE B 1.2.2 Introduction 50 1.2.3 Present work 52 1.2.4 Conclusion 54 1.2.5 Experimental 55 1.2.6 References 67 SECTION C: STUDIES DIRECTED TOWARDS SYNTHESIS OF AH-1763 Ila 1.3.0 Introduction 71 1.3.1 Present work 74 1.3.2 Experimental 84 1.3.3 References 96 CHAPTER II: SYNTHETIC STUDIES TOWARDS BENZOPHENONE PRECURSOR FOR BALANOL 97-177 General Introduction 97 SECTIONA: A REVIEW ON SYNTHESIS OF BALANOL AND ITS INTERMEDIATES PART I: SYNTHESES OF BENZOPHENONE DOMAIN OF BALANOL 101 PART 11: SYNTHETIC METHODS FOR HEXAHYDROAZEPINE PORTION OF BALANOL 108 PART III: DESIGN AND SYNTHESIS OF NEW ANALOGS OF BALANOL 117 SECTION B: SYNTHESIS OF BENZOPHENONE PRECURSOR FOR BALANOL 2.2.0 Introduction 122 2.2.1 Present work 122 2.2.3 Conclusion 145 2.2.4 Experimental 146 2.2.5 References 177 CHAPTER III: APPLICATIONS OF HETEROGENEOUS CATALYSTS IN ORGANIC TRANSFORMATIONS 180-204 General Introduction 180 SECTION A: REGIOSPECIFIC ACYLATION OF AROMATICS OVER HYDRATED ZIRCONIA 3.1.0 Introduction 181 3.1.3 Results and Discussion 183 3.1.4 Conclusion 186 3.1.5 Experimental 187 3.1.6 References 193 SECTION B: OXIDATION OF PRIMARY AND SECONDARY BENZYLIC ALCOHOLS AND SULFIDES OVER LaCoO3 USING 70°6 TBHP 3.2.0 Introduction 194 3.2.2 Results and Discussion 195 3.2.3 Conclusion 197 3.2.4 Experimental 198 3.2.5 References 204 SECTION C: SELECTIVE BENZYLIC OXIDATION OVER Mn -Zr USING 70% TBHP 3.3.0 Introduction 206 3.3.2 Results and Discussion 206 3.3.3 Conclusion 209 3.3.4 Experimental 211 3.3.5 References 213 LIST OF PUBLICATIONS: 214 GENERAL REMARKS 1. All the temperatures are in °C. All the melting points and boiling points are in °C and are uncorrected. 2. 1H NMR and 13C NMR spectra were recorded either on Brucker WH-90, Brucker AC- 200 or DRX-500 spectrometer in CDCl3 containing TMS as an internal standard with chemical shift (8) expressed in ppm downfield from TMS. The following abbreviations are used: s = singlet, d=doublet, t= triplet, q= quartet, m= multiplet and b= broad. 3. Infrared spectra (v max in cm-1) were recorded as either thin film or nujol mull or in CHCl3 on Perkin-Elmer Infra-red 683 B or 160S FT IR spectrometer with sodium chloride optics. 4. Mass spectra were recorded at an ionization energy of 70eV on Finnigan MAT -1020, Automated GGMS instrument. 5. All solvents and reagents were purified and dried by standard procedures. All evaporations were carried out under reduced pressure on Buchi rotary evaporator. 6. TLC was carried out on silica gel plates prepared by spreading the slurry (in CCI4) and drying at room temperature. The plates were analysed by keeping in iodine chamber. 7. Microanalysis was carried out in the micro analytical section of NCL. 8. GLC was carried out on Hewlett Packard 5890. 9. Column chromatography was performed on silica gel (60-120 mesh). Petroleum ether refers to the fraction boiling in the range of 60-80 °C. 10. The compound numbers, scheme numbers and reference numbers given in each chapter refers to that particular chapter only. ABBREVIATIONS Ac Acetyl Ar Aryl AIBN 2, 2'-Azobisisobutyronitrile l Allyl-B ( Ipc)2 l-Allyldiispinocampheylborane 9-BBN 9-Borabicyclo[3.3.1]nonane BnBr Benzyl bromide b.p. Boiling point tBuOH Tertiary butanol CSA Camphorsulfonic acid Cr-Zr Chromium stabilized zirconia Co-Zr Cobalt stabilized zirconia DBU 1, 8-Diazabicyclo[5.4.0]undec-7-ene DDQ 2,3-Dichloro-5,6-dicyano- 1,4-b~nzoquinone DEAD Diethyl azodicarboxylate DIBAL H Diisobutylaluminium hydride DMF Dimethylformamide DMAP 4-(Dimethylamino)pyridine DMS Dimethyl sulphate DMSO Dimethyl sulphoxide Et3Si H Triethyl silane g Gram/s hr Hour/s HMPA Hexamethylphosphoramide i pr2NH Diisopropylamine IR Infrared LiAlH4 Lithium aluminum hydride LiHMDS Lithium hexamethyldisilazane MsCI Mesyl chloride m-CPBA m-Chloroperoxybenzoic acid MOM-Cl Methoxymethylene chloride Mn-Zr Manganese stabilized zirconia M+ Molecular ion Min Minutes Me Methyl NBS N-bromosuccinimide Ni-Zr Nickel stabilized zirconia NMO 4-Methylmorpholine N-oxide NMR Nuclear magnetic resonance Ph Phenyl PhCCl3 Benzotrichoride PPA Polyphosphoric acid TBHP Tertiary butylhydrogen peroxide TBAF Tetrabutylammonium fluoride TBDMS Tertiary butyldimethylsilyl p-TSA p-Toluenesulphonic acid TEMPO 2,2,6,6-Tetramethylpiperidine-1-oxyl TFAA Trifluoroacetic anhydride TFA Trifluoroacetic acid TIPS Triisopropylsilane TLC Thin layer chromatography THF Tetrahydrofuran TMEDA N,N,N’,N’-Tetramethylethyle-nediamine TMS-CN Trimethylsilyl cyanide Thesis Abstract Thesis Title "Synthetic Studies on Balanol, Angucyclines and Catalytic Organic Transformations" The thesis has been divided into three chapters. Chapter I deals with the synthetic studies on angucyclines and contains three sections. Section A describes the synthesis of (+-)-brasiliquinone B. Section B contains attempted synthesis of brasiliquinone C and synthesis of (+-)-8-deoxybrasiliquinone B while section C deals with the synthetic approaches towards AH-1763 Ila. Chapter II deals with the studies towards synthesis of balanol, a novel protein kinase C inhibitor, which is subdivided into two sections. Section A covers literature review on balonol while section B describes synthesis of benzophenone precursor for balanol. Applications of heterogeneous catalysts for organic transformations are discussed in chapter III. This chapter is further divided into three sections. Section A deals with the regiospecific acylation of aromatics over hydrated zirconia whereas section B and C describe use of heterogeneous catalysts for oxidation reactions. Chapter I: Synthetic Studies on Angucycline Antibiotics This chapter is further divided into three sections. Section A: Synthesis of (t)-Brasiliquinone B Introduction Angucycline antibiotics are the class of benz(a)anthracene antibiotics possessing a typical tetracyclic structure having different groups at different positions. These are derived from the secondary metabolites of microorganisms. These compounds showed remarkable antimicrobial and antiviral activities. There are several reports on isolation and biological activities of these molecules but a very few attempts have been made to synthesize these bioactive molecules.
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