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Synthesis of Phosphine-Alkene Ligands and 3-Hydroxy Piperidines Using Organolithium Chemistry Chehasnah Haji-Cheteh

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Synthesis of Phosphine-Alkene Ligands and 3-Hydroxy Piperidines Using Organolithium Chemistry Chehasnah Haji-Cheteh Synthesis of Phosphine-Alkene Ligands and 3-Hydroxy Piperidines Using Organolithium Chemistry Chehasnah Haji-Cheteh Doctor of Philosophy University of York Chemistry March 2016 Abstract Abstract This thesis describes synthetic routes to P-stereogenic phosphine-alkene ligands and 3- hydroxy piperidines containing heteroaromatics via lithiation-trapping of phosphine boranes or N-Boc pyrrolidine. Both topics are introduced in chapter 1. Chapter 2 presents a route to a new type of P-stereogenic phosphine-alkene ligand B prepared by racemic lithiation of t-butyldimethylphosphine borane or dimethylphenylphosphine borane using s-BuLi. Different allylic halides were used to trap the lithiated R1 = Ph, t-Bu intermediate to give chiral alkene-phosphine boranes A. R2 = H, Me, Br In chapter 3, 3-hydroxy piperidines were synthesised from the ring expansion of hydroxy pyrrolidines. Two novel, short and simple synthetic routes were developed (as shown below). Lithiation-trapping reaction of N-Boc pyrrolidine C using pyridine carboxaldehydes gave N-Boc pyrrolidine alcohols syn-D and anti-D. On the other hand, an alternative approach to obtain 3-hydroxy piperidines anti-H starting from N-trityl prolinal E derived from (S)-proline was investigated. Addition of lithiated heteroaromatics, generated from a Br/Li exchange reaction, to N-trityl prolinal E diastereoselectively gave N-trityl alcohols anti-F. The Boc or trityl deprotection and reductive amination then gave N-benzyl pyrrolidines syn-G and anti-G. Finally, the ring expansion via an aziridinium ion of alcohols syn-G and anti-G gave 3-hydroxy piperidines syn-H and anti-H. The stereochemistry of 3- hydroxy piperidines syn-H and anti-H was proven using J-values in the 1H NMR spectra. 2 List of Contents List of Contents Abstract……………………………………………………………………………..2 List of Contents……………………………………………………………………..3 List of Tables………………………………………………………………………..5 Acknowledgements………………………………………………………………....6 Author’s Declaration………………………………………………………………..7 Chapter 1 Introduction………………………………………………………………..8 1.1 Introduction to Organolitium Reagents………………………………………..9 1.2 Overview of Lithiation-Trapping of Phosphine-Boranes……………………..10 1.3 Overview of Lithiation-Trapping of N-Boc Pyrrolidine………………………17 Chapter 2 Investigation of the Synthesis of P-Stereogenic Phosphine-Alkene Ligands………………………………………………………………………………..22 2.1 Introduction to Chiral Phosphine-Alkene Ligands……………………………23 2.2 Synthesis of Chiral Phosphine-Alkene Ligands………………………………25 2.3 Project Outline………………………………………………………………..35 2.4 Synthesis of Dimethylphosphine Boranes…………………………………….36 2.5 Racemic Lithiation of t-Butyl Dimethylphosphine Borane and Trapping with Allylic Halides under Different Conditions………………………………………..37 2.6 Racemic Lithiation of Phenyl Dimethylphosphine Borane and Trapping with Allylic Halides under Different Conditions………………………………………..45 2.7 Investigation of Borane Deprotection…………………………………………49 2.8 Aymmetric Lithiation of Phenyl Dimethylphosphine Borane and Trapping with Allyl Bromide………………………………………………………………...51 2.9 Synthesis of Dihomoallylic Phosphine Boranes………………………………53 2.10 Conclusions and Future Work………………………………………………..54 3 List of Contents Chapter 3 Investigation of New Routes to 2-Heteroaryl 3-Hydroxy Piperidines…57 3.1 Brief Introduction of New Routes to 3-Hydroxy Piperidines…………………58 3.2 Overview of Synthesis Routes to 3-Hydroxy Piperidnes……………………..59 3.3 Project Outline………………………………………………………………..77 3.4 Investgation of Synthetic Routes from N-Boc Pyrrolidine……………………78 3.4.1 Lithiation-Trapping of N-Boc Pyrrolidine………………………………..78 3.4.2 Reduction of N-Boc Pyrrolidinones………….……………………………84 3.4.3 Ring Expansion of N-Methyl Hydroxy Pyrrolidines to Piperidines……….91 3.4.4 Ring Expansion of N-Benzyl Hydroxy Pyrrolidines to Piperidines……….96 3.4.5 Proof of Stereochemistry of Hydroxy Pyrrolidines………………………104 3.4.6 Overview and Limitations of Initial Route………………………………107 3.5 Investigation of Synthetic Routes from (S)-Proline………………………….108 3.5.1 Synthesis and Reactions of N-Benzyl Pyrrolidinal and N-Benzyl Pyrrolidinones……………………………………………………….108 3.5.2 Synthesis of 3-Hydroxy Piperidines from N-Trityl Pyrrolidinal…………114 3.6 Conclusions and Future Work………………………………………………124 Chapter 4 Experimental…………………………………………………………….127 4.1 General Methods…………………………………………………………….127 4.2 General Procedures…………………………………………………………..128 4.3 Experimental for Chapter 2………………………………………………….131 4.4 Experimental for Chapter 3………………………………………………….151 Abbreviations………………………………………………………………………...213 Chapter 5 References……………………………………………………………….218 4 List of Tables List of Tables Table 1.1…………………………………………………………………………………...14 Table 1.2…………………………………………………………………………………...18 Table 1.3…………………………………………………………………………………...19 Table 2.1…………………………………………………………………………………...38 Table 2.2…………………………………………………………………………………...44 Table 2.3…………………………………………………………………………………...46 Table 2.4…………………………………………………………………………………...48 Table 2.5……………………………………………………………………………….......51 Table 3.1……………………………………………………………………………….......82 Table 3.2……………………………………………………………………………….......83 Table 3.3……………………………………………………………………………….......88 Table 3.4……………………………………………………………………………….......90 Table 3.5……………………………………………………………………………….......97 Table 3.6……………………………………………………………………………….......99 Table 3.7……………………………………………………………………………….....110 Table 3.8……………………………………………………………………………….....115 5 Acknowledgements Acknowledgements First of all, I would like to thank Prof. Peter O’Brien for the great opportunity to join this wonderful group. Without his encouragement and guidance, this research would not have been possible. In addition, I would like to thank Prof. Ian Fairlamb for his suggestions and the use of the ReactIR equipment. I would also like to thank Dr. John Slattery for his assistance and advice as my independent panel member. Next, I would like to thank all past and present members of the POB group for their friendliness and helpful lab-work suggestions. In no particular order, Giorgio, Xiao, Peter, Graeme, Dave, Mary, Giacomo, Sarah, Adam, Alice, Mickey, Masakazu and Will. I would also like to thank Peter and Joe from the Parsons group for making my time in the lab enjoyable as well. Additional thanks go to the Fairlamb group in particular to Charlotte for ReactIR advice, and the Taylor group for advice and loan of chemicals. The research presented in this thesis would not have been possible without considerable support from the technical staff in the Department of Chemistry. Thus, I would like to thank Steve and Mike from stores, Heather for the NMR service, Karl for mass spectrometry and Graeme McAllister for lab-work advice and maintenance of the dry solvents machine. I would like to thank all of my Thai friends, in particular to Nong and Fon, for sharing a good time during my PhD and being beside me every moment. I would also like to thank Angie Bell from the Open Door Team. Without her support, this research would not have been possible or have progressed. An addition acknowledgement goes to the Royal Thai Government for funding and support during my living in York. Finally, I would like to thank my beloved mum and dad, who are always with me through the highs and lows, give me unconditional love and have encouraged me throughout my stay in the U.K. 6 Author’s Declaration Author’s Declaration This research project in this thesis is my own and was carried out at the University of York between April 2011 and March 2016. This work is, to the best of my knowledge, original except where due reference has been made to other authors and/or co-workers. Part of this work has been reproduced in a published paper: Lüthy, M.; Wheldon, M. C.; Haji-Cheteh, C.; Atobe, M.; Bond, P. S.; O’Brien, P.; Hubbard, R. E.; Fairlamb, I. J. S.; Lead-oriented synthesis: Investigation of organolithium-mediated routes to 3-D scaffolds and 3-D shape analysis of a virtual lead-like library, Bioorg. Med. Chem. 2015, 23, 2680-2694. 7 Chapter 1 Introduction Chapter 1 Introduction This thesis contains research into the synthesis of two different types of heterocyclic structures. The first topic involved the design and synthesis of a new class of P-stereogenic phosphine-alkene ligands shown by phosphines 1 (Figure 1.1). The second topic concerned the development of new methodology for the synthesis of 2-aryl-3-hydroxy piperidines 2 (Figure 1.1). Although both target molecules 1 and 2 have very different structures, one of the key synthetic steps to each of them involved the use of strong organolithium bases such as n-BuLi and s-BuLi to carry out a lithiation or deprotonation step. In the phosphine project (Chapter 2), lithiation of phosphine boranes was used. In contrast, in the piperidines project (Chapter 3), N-Boc pyrrolidine 3 was lithiated, trapped and eventually ring-expanded. Figure 1.1 8 Chapter 1 Introduction 1.1 Introduction to Organolithium Reagents Over the past decades, organolithium reagents have continued to play an important role in modern organic synthesis. Due to their powerful basicity, most deprotonation chemistry makes use of organolithium reagents.1 A number of total syntheses of natural products and drug compounds make use of the wide range of organolitium reagents such as MeLi, n-BuLi, s-BuLi, t-BuLi and PhLi as strong bases. In the work described in this thesis, the commercially available reagents n-BuLi and s-BuLi were used to deprotonate the starting phosphine borane or N-Boc pyrrolidine to form the respective lithiated intermediates. Compared to s-BuLi, n-BuLi is less basic and less reactive. It is well known that
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