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Enaminones in the Synthesis of Azabicyclic Models for Alkaloids

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Enaminones in the Synthesis of Azabicyclic Models for Alkaloids ENAMINONES IN THE SYNTHESIS OF AZABICYCLIC MODELS FOR ALKALOIDS SIYANDA THABANI MTHEMBU FEBRUARY 2008 SUPERVISED BY PROF. J. P. MICHAEL AND PROF. C. B. DE KONING AN MSc DISSERTATION SUBMITTED TO THE FACULTY OF SCIENCE AT THE UNIVERSITY OF THE WITWATERSRAND,JOHANNESBURG IN FULFILMENT OF THE REQUIREMENTS FOR DEGREE OF MASTER OF SCIENCE DECLARATION I declare that this work presented in this dissertation was carried out exclusively by me under the supervision of Prof. J. P. Michael and Prof. C. B. de Koning and with the assistance of the acknowledged individuals. It is being submitted for the degree of Master of Science in the University of the Witwatersrand, Johannesburg. It has not been submitted before for any degree or examination in any other University Siyanda Thabani Mthembu February 2008 i ABSTRACT The purpose of this project was to investigate whether methodology developed in these laboratories for preparing 5/6 and 6/6 azabicyclic systems with bridged head nitrogen can be extended to 7/6, 8/6, 9/6 and 13/6 azabicyclic systems. The methodology entails the use of enaminones as central to the formation of the azabicyclic systems. The synthetic route adopted began with the Beckmann rearrangement reaction and/or the Schmidt reaction of cyclic ketones to make lactams, which were then thionated by Curphy or Brillon procedures. The Michael reaction of NH thiolactams with tert -butyl acrylate was followed by Eschenmoser sulfide contraction to afford the enaminones 132 which were utilised in the ring-closing step. This involved hydrolysis of the tert -butyl ester and cyclisation via a mixed anhydride. Ethyl 7-oxo-1,2,3,5,6,7-hexahydroindolizine-8-carboxylate 170b , 1-(4- nitrobenzoyl)-3,4,6,7,8,9-hexahydroquinolizin-2-one 172a , 1-benzoyl- 3,4,7,8,9,10-hexahydropyrido[1,2-a]azepin-2(6 H)-one 173d , 1-(4-nitrobenzoyl)- 3,4,6,7,8,9,10,11-octahydropyrido[1,2-a]azocin-2-one 174a , and 1-(4- nitrobenzoyl)-3,4,7,8,9,10,11,12,13,14,17,16-dodecahydropyrido[1,2-a]azacyclo- tridecin-2(6 H)-one 176a were synthesised in good yields, but yields of 8-(4- nitrobenzoyl)-2,3,5,6-tetrahydroindolizin-7(1 H)-one 171a and 1-(4-nitrobenzoyl)- 3,4,7,8,9,10,11,12-octahydropyrido[1,2-a]azonin-2(6 H)-one 175a were not satisfactory. In a much shorter synthetic route that involves enaminone chemistry as well, NH vinylogous amides were synthesised by the Eschenmoser sulfide contraction and used in the aza-annulation reaction with acryloyl chloride. Structural isomers (to compounds mentioned above) 8-(4-nitrobenzoyl)-2,3,6,7-tetrahydroindolizin- 5(1 H)-one 178a , 1-(4-nitrobenzoyl)-2,3,7,8,9,10-hexahydropyrido[1,2-a]azepin- 4(6 H)-one 180a , 1-benzoyl-2,3,7,8,9,10-hexahydropyrido[1,2-a]azepin-4(6H)-one 180b , 1-(4-nitrobenzoyl)-2,3,6,7,8,9,10,11-octahydropyrido[1,2-a]azocin-4-one ii 181a , 1-(4-nitrobenzoyl)-2,3,7,8,9,10,11,12-octahydropyrido[1,2-a]azonin-4(6 H)- one 182a and 1-(4-nitrobenzoyl)-2,6,7,8,9,10,11,12,13,14,15,16- dodecahydropyrido[1,2-a]azacyclo-tridecin-4(3 H)-one 183a were synthesised in good yields. 1-(4-Nitrobenzoyl)-2,3,6,7,8,9-hexahydroquinolizin-4-one 179a was obtained in low yield, and apparently as two conformational isomers. iii ACKNOWLEDGEMENTS I would like to acknowledge the following individuals for their contribution towards the success of this project. • Prof. J. P. Michael for intellectual and financial support • Prof. C. B. de Koning for intellectual support • The NRF for financial support • Mr R. Mampa for all NMR data and his patience • Mr M. Brits and Dr. A. Dinsmore for all MS data • Mr G. Morgans for his support • The organic group for the good working environment • My mother for her love and support • God for ALL iv TABLE OF CONTENTS CHAPTER 1: BACKGROUND TO THE PROJECT .................................................1 1.1 Introduction ........................................................................................................1 1.2 Alkaloids with seven and larger-membered rings...............................................2 1.2.1 Lehmizidines...................................................................................................2 1.2.2 Stemona alkaloids...........................................................................................3 1.2.3 Securinega alkaloids.......................................................................................7 1.2.4 Manzamine alkaloids ......................................................................................9 1.3 Reported synthetic approaches to pyrrolo[1,2-a]azepine and pyrido[1,2- a]azepine systems: selected examples..................................................................11 1.3.1 A short synthesis of racemic (3,10 Z)-3-butyllehmizidine 56 and (3,10 E)-3- butyllehmizidine 14 ................................................................................................11 1.3.2 Mercury-promoted Schmidt reactions ...........................................................12 1.3.3 Novel synthesis of octahydro-1H-pyrrolo[1,2-a]azepine and decahydropyrido[1,2-a]azepine..............................................................................15 1.3.4 Synthesis of 5/7-, 5/8- and 5/9-bicyclic lactams ............................................16 1.4 The Wits Background.......................................................................................19 1.4.1 Introduction to enaminones...........................................................................19 1.4.2 Alkaloid synthesis via enaminones: Selected Wits examples .......................22 1.5 Aims.................................................................................................................29 CHAPTER 2: RESULTS AND DISCUSSION ........................................................33 2.1 Synthesis of azacyclotridecane-2-one by the Beckmann rearrangement ........33 2.2 Synthesis of lactams by the Schmidt reaction..................................................34 2.3 Synthesis of NH thiolactams ............................................................................36 2.3.1 Synthesis by the Curphey procedure ............................................................36 2.3.2 Synthesis by the Brillon procedure................................................................39 2.4 Synthesis of N-alkylated thiolactams ...............................................................40 2.5 Eschenmoser sulfide contraction .....................................................................44 2.5.1 Synthesis of N-alkyl vinylogous urethanes....................................................44 2.5.2 Synthesis of N-alkyl vinylogous amides ........................................................48 v 2.5.3 Synthesis of NH vinylogous amides..............................................................51 2.6 Synthesis of azabicyclic systems by intramolecular cycloacylation..................54 2.7 Synthesis of azabicyclic systems by aza-annulation........................................60 2.8 Conclusion .......................................................................................................65 2.9 Future work......................................................................................................67 CHAPTER 3...........................................................................................................71 3.1 General experimental methods........................................................................71 3.2 General procedure for synthesizing lactams using the Beckmann rearrangement method ..........................................................................................72 3.3 General procedure: The Schmidt reaction .......................................................73 3.4 Thionation of lactams.......................................................................................75 3.4.1 The Curphey procedure ................................................................................75 3.4.2 The Brillon procedure....................................................................................75 3.5 General procedure for the N-alkylation of thiolactams with acrylate asters......79 3.6 General procedure for the preparation of N-alkyl vinylogous urethanes from N- alkylthiolactams......................................................................................................83 3.7 General procedure for the preparation of N-alkyl vinylogous amides from N- alkylthiolactams......................................................................................................89 3.8 General procedure for the preparation of NH vinylogous amides from thiolactams.............................................................................................................96 3.9 Synthesis of azabicyclic systems by intramolecular cycloacylation................101 3.10 Reactions of N-H vinylogous amides with acryloyl chloride .........................108 REFERENCES ....................................................................................................115 APPENDIX: NMR DATA ......................................................................................119 vi CHAPTER 1: BACKGROUND TO THE PROJECT 1.1 Introduction The organic group at the University of the Witwatersrand (Wits) has devoted considerable effort to making azabicyclic alkaloids containing the indolizidine 1 and quinolizidine 2 ring systems, which are very common in natural products. Other azabicyclic systems such as 3 and 4 are much less common in nature, and the Wits research group has paid almost no attention to them up to
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