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Synthetic Studies Towards Camptothecin, Its Analogues and Other Biologically Active Compounds

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Synthetic Studies Towards Camptothecin, Its Analogues and Other Biologically Active Compounds SYNTHETIC STUDIES TOWARDS CAMPTOTHECIN, ITS ANALOGUES AND OTHER BIOLOGICALLY ACTIVE COMPOUNDS A THESIS Submitted to the UNIVERSITY OF PUNE For the degree of DOCTOR OF PHILOSOPHY in CHEMISTRY by ASHOK B. PATHAK Research supervisor DR. SUBHASH P. CHAVAN Division of Organic Chemistry National Chemical Laboratory Pune 411 008, INDIA MARCH 2008 NATIONAL CHEMICAL LABORATORY (Council of Scientific & Industrial Research) Dr. Homi Bhabha Road, Pune-411 008. India. Dr. Subhash P. Chavan Scientist F Division of Organic Chemistry Phone: +91-20-25902289 Fax: +91-20-25902629 E-mail: [email protected] CERTIFICATE This is to certify that the work incorporated in the thesis entitled “Synthetic Studies Towards Camptothecin, Its Analogues And Other Biologically Active Compounds” submitted by Mr. Ashok B. Pathak was carried out by him under my supervision at National Chemical Laboratory, Pune. Material that has been obtained from other sources is duly acknowledged in this thesis Date: Subhash P. Chavan (Research Supervisor) DECLARATION I hereby declare that the thesis entitled “Synthetic Studies Towards Camptothecin, Its Analogues And Other Biologically Active Compounds” submitted for Ph. D. degree to the University of Pune has been carried out at National Chemical Laboratory, under the supervision of Dr Subhash P. Chavan. This work is original and has not been submitted in part or full by me for any degree or diploma to this or any other university. Date: Ashok B. Pathak Division of Organic Chemistry National Chemical Laboratory Pune-411 008, India. Dedicated To My Family and Teachers Contents Page No. Acknowledgements i General Remarks ii Abbreviations iii Abstract vi Chapter 1 Section-I General introduction of camptothecin 1.1.1 Introduction 1 1.1.2 Isolation, properties and structural elucidation 2 1.1.3 Naturally occurring camptothecins and its sources 3 1.1.4 Biogenesis 6 1.1.5 Mode and Mechanism of Action 8 1.1.6 Structure-Activity Relationship Study 11 1.1.7 Brief literature survey 16 1.1.8 References 26 Section-II General account on metathesis 1.2.1 Introduction 31 1.2.2 Catalysts 32 1.2.3 Mechanisms 32 1.2.4 Types of metathesis 37 1.2.6 Reference 44 Section-III Studies towards synthesis of camptothecin and its analogues employing tandem ethylene cross enyne metathesis and RCM 1.3.1 Introduction 46 1.3.2 Present work 46 1.3.3 Results and discussion 47 1.3.4 Conclusion 56 1.3.5 Experimental 57 1.3.6 Spectra 68 1.3.7 References 85 Chapter 2 Section-I Total synthesis of (±)-camptothecin employing tandem Knoevenagel condensation and Michael addition 2.1.1 Introduction 87 2.1.2 Present work 87 2.1.3 Results and discussion 88 2.1.4 Conclusion 96 2.1.5 Experimental 97 2.1.6 Spectra 105 2.1.7 References 116 Section-II Total synthesis of (+)-camptothecin employing Pd- catalyzed cyclization strategy 2.2.1 Introduction 117 2.2.2 Present work 117 2.2.3 Results and discussion 118 2.2.4 Conclusion 130 2.2.5 Experimental 131 2.2.6 Spectra 140 2.2.7 References 153 Section-III Formal synthesis of (±)-camptothecin 2.3.1 Introduction 155 2.3.2 Present work 155 2.3.3 Results and discussion 156 2.3.4 Conclusion 169 2.3.5 Experimental 170 2.3.6 Spectra 187 2.3.7 References 211 Chapter 3 Section-I Synthesis of 3-ethyl-4-methyl pyrroline-2-one 3.1.1 Introduction 212 3.1.2 Literature survey 213 3.1.3 Present work 214 3.1.4 Results and discussion 215 3.1.5 Conclusion 223 3.1.6 Experimental 224 3.1.7 Spectra 233 3.1.8 References 246 Section-II Total synthesis of (Z)-pulchellalactam 3.2.1 Introduction 247 3.2.2 Literature survey 247 3.2.3 Present work 251 3.2.4 Results and discussion 251 3.2.5 Conclusion 258 3.2.6 Experimental 259 3.2.7 Spectra 266 3.2.8 References 278 Section-III Total synthesis rubrolide E 3.3.1 Introduction 279 3.3.2 Literature survey 280 3.3.3 Present work 283 3.3.4 Results and discussion 284 3.3.5 Conclusion 291 3.3.6 Experimental 292 3.3.7 Spectra 300 3.3.8 References 313 Acknowledgements First of all I wish to express my deep sense gratitude and respect to my research supervisor Dr. Subhash P. Chavan, for introducing me the fascinating field of Organic chemistry, his valuable guidance and helpful suggestions throughout my Ph.D. programme. It is my pleasant duty to express my grateful and sincere thanks to Dr. U. R. Kalkote and Dr. S. K. Kamat for their valuable co-operation during this work. I am also thankful to Dr. M. K. Gurjar (former head, OCT), Dr. Ganesh Pandey (Head, Division of Organic Chemistry) and Dr. S. Sivaram (Director, NCL) for permitting me to work in NCL. My thanks are due to Dr. Mrs. R. D. Wakharkar, Mrs. Latha Sivadasan, Dr. R. A. Joshi, Dr. Mrs. R. R. Joshi, Dr. H. B. Borate, Dr. C. V. Ramana, Dr. S. Hotha, Dr. N. N. Joshi, Mr. I. Shivakumar, Dr. Muthukrishnan, Dr. Mohapatra, Dr. Ramalingam and all other scientists of NCL and Prof. D. D. Dhavale is gratefully acknowledged. I would also like to acknowledge all the staff members of GC, HPLC, IR, NMR, Mass, Microanalysis, X-ray analysis, Library, Administration and technical divisions of NCL for their assistance during the course of my work. I take this opportunity to thank to my seniors as well as present labmates Dr. Sivappa, Dr. Shivsankar, Dr. Rajendra, Dr. Ramesh, Dr. Pasupathy, Dr. Priti, Dr. Sambhaji, Dr. Dushyant, Dr. Praveen, Dr. Ramakrishna, Dr. Pallavi, Dr. Mahesh, Sanjay, Sapna, Sudhir, Manoj, Vikas, Sharad, Abasaheb, Ganesh, Shankar, Dynaneshwar, Lalit, Kishor, Ankur, Makarand, Surfaraj, Nilesh, Sumant, Pradip and Prakash is gratefully acknowledged. They made working in the lab enjoyable. I wish to thank division office staff, Mrs. Catherine, Mrs. Kulkarni, Mr. Fernandis, Mr. Ranawade, Mr. Tikhe, and Mr. Rajgopal and for their help whenever needed. My thanks are due to all my friends of NCL as well as out of NCL for their sincere co-operation. I am also thankful to my parents, family members, relatives and teachers who have contributed a lot for me to reach this stage. The love and support from my wife Mrs. Surekha and daughter Miss. Aditi for the healthy and inspiring environment with out whom I would not been able to stand out as a person and my deep sense of gratitude remains forever. The thesis is a form to pay respect to their attributes. Last but not least, I am thankful to CSIR, New Delhi for fellowship. NCL, Pune Ashok B. Pathak i General Remarks 1. All melting points and boiling points are uncorrected and the temperatures are in the centigrade scale. 2. The compound numbers, scheme numbers and reference numbers given in each section refers to that particular section only. 3. All solvents were distilled before use. Petroleum ether refers to the fraction boiling in the range of 60-80oC. 4. Solvents for anhydrous reaction were prepared according to the procedures reported in Perrin’s book. 5. TLC analysis was carried out using thin layer plates pre-coated with silica gel 60 F254 (Merck) and visualized by fluorescence quenching or Iodine or by charring after treatment with p-anisaldehyde. 6. In cases where chromatographic purification was done, silica gel (230-400 mesh) was used as the stationary phase or otherwise as stated. 7. IR spectra were recorded on Perkin-Elmer Infrared Spectrophotometer Model 68B or on Perkin-Elmer 1615 FT Infrared spectrophotometer. 8. 1H NMR and 13C NMR were recorded on Bruker AC-200 (50 MHz) or Bruker MSL-300 (75 MHz) or Bruker AV-400 (100 MHz) or Bruker DRX-500 (125 MHz). Figures in parentheses refer to 13C frequencies. Tetramethylsilane was used as the internal standard. 9. GCMS were recorded on Shimadzu’s GCMS-QP5050-A. 10. Mass spectra were recorded at ionization energy 70eV on Finnigan MAT-1020, automated GC/MS instrument and on API Q STARPULSAR using electron spray ionization [(ESI), solvent medium, a mixture of water, acetonitrile and ammonium acetate] technique and mass values are expressed as m/z. 11. Starting materials were obtained from commercial sources or prepared using known procedures. 12. Microanalytical data were obtained using a Carlo-Erba CHNS-O EA 1108 Elemental analyzer within the limits of accuracy (± 0.4%) ii Abbreviations Ac Acetyl AIBN 2,2-Azobis(isobutyronitrile) AIDS Acquired Immuno deficiency syndrome Ar Aromatic aq Aqueous BBr3 Borane tribromide Bn Benzyl BOC tert-Butoxycarbonyl n-BuLi normal butyllithium sBu secondary butyl tBu tertiary butyl Bz Benzoyl CAN Ceric ammonium nitrate Cat. Catalytic Cbz Carbobenzyloxy CM Cross metathesis COM Cross olefin metathesis CPT Camptothecin oC Temperature in degrees Centigrade DBU 1,8-Diazabicyclo[5,4,0]undec-7-ene DCC 1,3-Dicyclohexylcarbodiimide DCM Dichloromethane DDQ 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone DEAD Diethyl azodicarboxylate DEPT Distortionless Enhancement by Polarization Transfer DHP Dihydropyran (DHQD)2-PYR Dihydroquinidine diphenylpyrimidine DIBAL-H Diisobutylaluminium hydride DMAP 4-Dimethylaminopyridine DMB Dimethoxy benzyl DME Dimethoxy ethane DMF N,N-Dimethylformamide iii DMS Dimethyl sulphate DMSO Dimethyl sulfoxide DNA Deoxyribonucleic acid equiv (eq) Equivalent Et Ethyl Et3N Triethyl amine EtOAc Ethyl acetate EtOH Ethyl alcohol g gram/s GCMS Gas Chromatograph Mass Spectrometer h hour/s HMPA Hexamethylphosphoramide HMDS Hexamethyldisilazane IR Infrared LA Lewis acid LAH Lithium Aluminium Hydride LDA Lithium diisopropyl amide mCPBA meta-Chloroperbenzoic acid Me Methyl MF Molecular formula mL millilitre/s mmol millimole MOM methoxymethyl m.p.
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