Phosphine-porphyrin conjugates : a thesis presented in partial fulfilment of the requirements for the degree of Masterate of Science in Chemistry at Massey University, New Zealand

The research carried out in this thesis comprises an investigation into the synthesis and characterisation of a variety of complexed phosphine-aldehydes, complexed phosphinoporphyrins, and phosphinoferrocene conjugates. The porphyrin and phosphine moieties are linked together via the vinyl group, a product of Wittig chemistry. In general, functionalisation occurs at the β-pyrrolic position of the porphyrin and at the para position of a phenyl group on the phosphine. Chapter One introduces the properties of porphyrins and the triphenylphosphine ligand, as well as a brief review on the types of functionalised triphenylphosphines. A brief review of existing phosphinoporphyrins is also discussed. The proposal for using the vinylic linking group (and hence Wittig chemistry) to connect the porphyrin and the phosphine moieties is also described. Chapter Two outlines the synthesis of the 4-(diphenylphosphino)benzaldehyde (5) ligand, which is a necessary precursor for the Wittig reaction with meso-tetraphenylporphyrin (TPP) phosphonium salt (1). It was discovered that the Wittig reaction of (1) with (5) led to the synthesis of the product of oxidation, phosphinoporphyrin oxide (7), instead of the desired phosphinoporphyrin (6). Therefore an alternative scheme was pursued - complexation before the Wittig reaction. Hence the remainder of the chapter describes both the synthesis and characterisation aspects of five transition metal complexes of (5). These include complexes of gold, ruthenium, tungsten, and platinum. Chapter Three describes the synthesis and characterisation of a variety of novel complexed phosphinoporphyrins, including two bis-phosphinoporphyrin complexes. This was achieved by utilising Wittig chemistry of TPP phosphonium salt (1) with the appropriate complexed phosphine-aldehyde. In each case, optimisation of the Wittig conditions was required in order to obtain the sterically and thermodynamically favoured trans isomer. Chapter Four extends the phosphinoporphyrin chemistry by investigating the synthesis of a novel phosphinoporphyrin trimer. In order to achieve this, a phosphine tris-aldehyde was synthesised. This chapter focuses on the synthesis and characterisation of tris(4-formylphenyl)phosphine oxide (20). The results of the Wittig reaction of (20) with TPP phosphonium salt (1) are also described. Chapter Five demonstrates the versatility of both the Wittig and phosphine chemistry. In this chapter, the synthesis of phosphinoferrocenes via Wittig chemistry is investigated. The ferrocene and phosphine moieties are linked via the vinyl group, in a similar manner as the phosphinoporphyrins. In this case, functionalisation occurs at the para position of a phenyl group of the phosphine to the cyclopentadienyl ring of the ferrocene. A phosphinoferrocene monomer, (24), was synthesised by Wittig reaction of a ferrocene phosphonium salt (22) with (5). Both the synthesis and characterisation of this compound is reported. Also described is the attempted synthesis of a phosphinotrisferrocene via Wittig reaction of (22) with (20). Chapter Six contains a brief summary of the results obtained during this study, and also mentions future research to be pursued in this field of study

Organic Reactions Promoted by Metal-Free Organic Dyes Under Visible Light Irradiation

Although dyes have received much attention as the visible light-activated photocatalysts, the use of metal-free organic dyes in synthetic organic chemistry is still limited. This chapter summarizes the recent progress in the visible light photocatalysis promoted by metal-free organic dyes. Eosin Y is the typical organic dyes to induce the photoredox catalysis. Recently, other organic dyes such as Rose Bengal, fluorescein, and methylene blue have been studied as photocatalysts to promote the single-electron transfer processes

Microwave-assisted phospha-Michael addition reactions on 13αestrane core

Novel 16-modified 13 α-estrone derivatives were synthesized via phospha-Michael addition reactions. Transformations of steroidal α,β-unsaturated ketons were carried out under different conditions in a microwave (MW) reactor. The antiproliferative activities of the newly synthesized compounds against a range of human adherent cancer cell lines (SCC-131, SCC154, Hela, SiHa, C33A, A2780, MCF-7, MDA-MB-231, T47D) were investigated by means of MTT assays. Certain potent derivatives were identified

Hydrophosphinylation of Styrenes Catalysed by Well‐Defined s‐Block Bimetallics

Advancing the applications of s-block heterobimetallic complexes in catalysis, we report the use of potassium magnesiate (PMDETA)2K2Mg(CH2SiMe3)4 [PMDETA=N,N,N’,N’,N’’-pentamethyldiethylenetriamine] for the catalytic hydrophosphinylation of styrenes under mild conditions. Exploiting chemical cooperation, this bimetallic approach offers greater catalytic activity and chemoselectivity than the single-metal components KCH2SiMe3 and Mg(CH2SiMe3)2. Stoichiometric studies between (PMDETA)2K2Mg(CH2SiMe3)4 and Ph2P(O)H help to elucidate the constitution of the active catalytic species, and illustrate the influence of donors on the potassium cation coordination, and how this may impact catalytic activity. Mechanistic investigations support that the rate determining step is the insertion of the olefinic substrate

The Reactivity of Ditetrelenes Towards Organophosphorus Oxides

The reactivity of tetramesityldisilene 4 and tetramesityldigermene 5 towards organophosphorus oxides was explored in this thesis. The reaction of dialkyl and diarylphosphine oxides and phosphites with ditetrelenes 4 and 5 resulted in a 1,3-addition to form diorganodisilyl and digermyl phosphinites 27, 28, 31, 32 and disilyl phosphites 35 and 36. The 1,3-addition resulted in a mild two electron reduction of the P(V) centre of the phosphine oxide and phosphite to a P(III) centre in the products, without the use of heat or a catalyst. The reaction of organophosphorus oxides provides another example of a main group oxide that can be activated by ditetrelenes 4 and 5 in addition to nitro and sulfonyl containing compounds, CO and CO2. The mechanism for the reaction of diorganophosphorus oxides and phosphites with ditetrelenes 4 and 5 was investigated through deuterium labelling studies and KIE experiments. The mechanism for the formation of disilyl and digermyl phosphinites and phosphites was determined to proceed through a nucleophilic addition. An exchange phenomenon between the OP(pentyl)2 moiety of 32 and an OPPh2 group from diphenylphosphine oxide was discovered and insights into the mechanism of this exchange were obtained

Scalable Rhodium(III)-Catalyzed Aryl C-H Phosphorylation Enabled by Anodic Oxidation Induced Reductive Elimination.

Transition metal catalyzed C-H phosphorylation remains an unsolved challenge. Reported methods are generally limited in scope and require stoichiometric silver salts as oxidants. Reported here is an electrochemically driven RhIII -catalyzed aryl C-H phosphorylation reaction that proceeds through H2 evolution, obviating the need for stoichiometric metal oxidants. The method is compatible with a variety of aryl C-H and P-H coupling partners and particularly useful for synthesizing triarylphosphine oxides from diarylphosphine oxides, which are often difficult coupling partners for transition metal catalyzed C-H phosphorylation reactions. Experimental results suggest that the mechanism responsible for the C-P bond formation involves an oxidation-induced reductive elimination process

Direct asymmetric reduction of levulinic acid to gamma-valerolactone: synthesis of a chiral platform molecule

Levulinic acid was directly converted to optically active (S)-gamma-valerolactone, a proposed biomass-based chiral platform molecule. By using a SEGPHOS ligand-modified ruthenium catalyst in methanol as a co-solvent, eventually, 100% chemoselectivity, and 82% enantioselectivity were achieved. The effect of the catalyst composition and reaction parameters on the activity and selectivity was investigated in detail. The conversion of a “real” biomass derived levulinic acid to optically active GVL without decreasing the enantioselectivity was also demonstrated

Manganese(i)-catalyzed access to 1,2-bisphosphine ligands

Chiral bisphosphine ligands are of key importance in transition-metal-catalyzed asymmetric synthesis of optically active products. However, the transition metals typically used are scarce and expensive noble metals, while the synthetic routes to access chiral phosphine ligands are cumbersome and lengthy. To make homogeneous catalysis more sustainable, progress must be made on both fronts. Herein, we present the first catalytic asymmetric hydrophosphination of α,β-unsaturated phosphine oxides in the presence of a chiral complex of earth-abundant manganese(i). This catalytic system offers a short two-step, one-pot synthetic sequence to easily accessible and structurally tunable chiral 1,2-bisphosphines in high yields and enantiomeric excess. The resulting bidentate phosphine ligands were successfully used in asymmetric catalysis as part of earth-abundant metal based organometallic catalysts

Study on new methods for the synthesis of benzo[b]phosphole oxides

磷杂环类化合物在有机合成、医药和材料科学等领域广泛应用，其中，苯并磷杂环戊二烯类化合物，一类结构类似氮杂环吲哚的磷杂环化合物，因其独特的物理光电性能，已经成为有机共轭杂环体系中不可缺少的一员，并在有机光电材料领域具有巨大应用潜力。目前，合成此类化合物的已知方法较少。因此，开发出新颖、高效的方法构建苯并磷杂环戊二烯类衍生物至关重要。 本文发展了两类简单易操作的构建多官能团的苯并磷杂环戊二烯类化合物的新方法，主要内容如下： 第一部分：发展了由廉价的无机盐过硫酸钾K2S2O8催化促进磷自由基生成与内炔试剂加成环化构建多样化的苯并磷杂环戊二烯类化合物的方法。该方法反应条件温和，操作简单，同时创新性...Phosphorus-containing heterocycles have wide applications in organic synthesis, medicinal chemistry, and material industries. Among these compounds, the phosphorous analogue of nitrogen heterocyclic indole, benzo[b] phospholes have become indispensable organic conjugated heterocyclic system and huge potential in the field of organic photoelectric materials because of their inherent physical and op...学位：工程硕士院系专业：化学化工学院_化学工程学号：2062014115144