锰试剂在有机合成中的应用

主要综述了近年来有机锰化合物及单质锰直接参与的有机反应有机合成中的应用。     

钨卡宾络合物在有机合成中的应用

对钨卡宾络合物参与的反应机理和一些合成方法作了简要的介绍,并评述了部分钨卡宾络合物合成有机化合物的反应。     

超声波在金属参与的有机合成方面的应用

综述了近十几年来超声波在金属参与的有机合成中的一些应用，参考文献44 篇。     

Applications of bismuth(III) compounds in organic synthesis

This review article summarizes the applications of bismuth(III) compounds in organic synthesis since 2002. Although there are an increasing number of reports on applications of bismuth(III) salts in polymerization reactions, and their importance is acknowledged, they are not included in this review. This review is largely organized by the reaction type although some reactions can clearly be placed in multiple sections. While every effort has been made to include all relevant reports in this field, any omission is inadvertent and we apologize in advance for the same (358 references).     

Dendrimers and hyperbranched polymers as high-loading supports for organic synthesis

Polymeric supports have become a big necessity for automated synthesis and combinatorial chemistry, yet, the loading capacities of most polystyrene resins are very limited (typically < 1.5 mmol x g(-1)). Dendrimers and hyperbranched polymers have been discussed for this application and now became readily available. These soluble polymers can either be used directly as high-loading supports for substrates, reagents, and catalysts or alternatively in hybrid polymers linked to conventional polystyrene resins.     

Preparation of new microgel polymers and their application as supports in organic synthesis

A series of soluble microgel polymers have been synthesized using solution-phase polymerization reactions. In a systematic manner, several variables such as monomer concentration, cross-linker content, reaction solvent and reaction time were examined, and this provided an optimal polymer with both solubility and precipitation characteristics suitable for synthetic applications. Thus, a chemically functionalized microgel polymer was synthesized, and the utility of this polymer in the synthesis of a small array of oxazole compounds has been demonstrated. The advantage of the microgel polymers produced was that they exhibited solution viscosities lower than those of conventional linear polymers even at higher concentrations, and this was found to be beneficial for their precipitation properties. Compounds prepared using the described microgel polymer supports were obtained in similar yields and purity when compared with insoluble resins, and more importantly, the soluble polymer bound intermediates could be analyzed at each step using standard NMR techniques.     

Optimised hydrothermal synthesis of multi-dimensional hybrid coordination polymers containing flexible organic ligands

In this paper, we summarise our recent research interest in the hydrothermal synthesis and structural characterisation of multi-dimensional coordination polymers. The use of N-(phosphonomethyl)iminodiacetic acid (also referred to as H₄pmida) in the literature as a versatile chelating organic ligand is briefly reviewed. This molecule plays an important role in the formation of centrosymmetric dimeric [V₂O₂(pmida)₂]⁴⁻ anionic units, which were first used by us as building blocks to construct novel coordination polymers. Starting with [V₂O₂(pmida)₂]⁴⁻ in solution, we have isolated [M₂V₂O₂(pmida)₂(H₂O)₁₀] species (where M²⁺ = Mn²⁺, Co²⁺ or Cd²⁺) via the hydrothermal synthetic approach, which were then employed for the construction of [CdVO(pmida)(4,4′-bpy)(H₂O)₂]·(4,4′-bpy)_0.5·(H₂O), [CoVO(pmida)(4,4′-bpy)(H₂O)₂]·(4,4′-bpy)_0.5, [Co(H₂O)₆][CoV₂O₂(pmida)₂(pyr)(H₂O)₂]·2(H₂O) and [Cd₂V₂O₂(pmida)₂(pyr)₂(H₂O)₄]·4(H₂O) by the inclusion of bridging organic ligands in the reactive mixtures, such as pyrazine (pyr) and 4,4′-bipyridine (4,4′-bpy). These materials can contain channel systems, and exhibit magnetic behaviour, not only due to the V⁴⁺ centres but also to the transition metal centres which establish the links between neighbouring dimeric [V₂O₂(pmida)₂]⁴⁻ anionic units. A closely related anionic moiety, [Ge₂(pmida)₂(OH)₂]²⁻, was engineered to allow the study of such crystalline hybrid materials using one- and two-dimensional high-resolution solid-state NMR.     

Applications of counter-current chromatography in organic synthesis purification of heterocyclic derivatives of lapachol

This work describes the application of counter-current chromatography (CCC) as a useful, fast and economic alternative for the isolation and purification of heterocyclic derivatives from lapachol and beta-lapachone, two naturally occurring compounds from Tabebuia species, and nor-beta-lapachone, a synthetic congener of lapachol. The discussed data comprise four examples of purification of synthetic reactions with different solvent systems - the mixture of the oxazole and the imidazole from beta-lapachone; the quinoxaline from nor-beta-lapachone; and the purification of the N-oxides from the quinoxaline and the phenazine from nor-beta-lapachone from their respective not fully reacted substrates by means of aqueous reversed- and normal-phase elution modes and non-aqueous solvent systems. Traditional purification of these reaction products by silica gel column chromatography demanded a large amount of solvent and time and, in some cases, serious degradation of the products occurred, leading to low yield of the reaction. High-speed counter-current chromatography (HSCCC) was used as an alternative to optimize the process and raise the yield of the reactions.     

Stealth star polymers: a new high-loading scaffold for liquid-phase organic synthesis

[formula: see text] Polyethylene glycol (PEG) has proven to be a versatile soluble-polymer support for organic synthesis, though the use of PEG has been limited by its relatively low loading (0.5 mmol/g or less). We have developed a new high-loading (1 mmol/g) soluble-star polymer based on a cyclotriphosphazene core with PEG arms that exhibit superior precipitation properties compared with those of linear PEG. Additionally, the heterocyclic core does not add interfering signals to the 1H or 13C NMR.     

Electrochemistry of conjugated organic polymers

The electrochemistry of conjugated organic polymers such as polyaniline, polythiophene, and polypyrrole has been reviewed. The physical chemistry and, especially, the electrochemistry of conducting polymers (CP) are largely determined by their electrosynthesis conditions. The effects of such factors as the dopant, solvent, and base electrolyte on the preparation and electrochemical n- and p-doping of CP have been considered. The outstanding features of the electrochemistry of CP have been delineated. The prospects for the use of CP as active cathode and anode materials in chemical cells have been discussed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 30, No. 3, pp. 111–129, May–June, 1994.     

Modified cubic spherosilicates as macroinitiators for the synthesis of inorganic–organic starlike polymers

Modified cubic spherosilicate cages of the type [Si₈O₂₀]^8? were used as rigid, inorganic cores for the synthesis of macroinitiators for thermal and photoinduced free radical and controlled radical polymerizations. Two different routes to these macroinitiators were investigated: the direct modification of the octaanion with chlorosilane‐functionalized initiators and the hydrosilation of SiH‐substituted cages. The latter synthesis of the macroinitiators resulted in more defined reaction products. With these compounds, the polymerizations of styrene and methyl methacrylate were carried out. The free radical polymerizations showed broad polydispersities based on coupling reactions, whereas the copper‐mediated atom transfer radical polymerizations (ATRP) revealed that good polymerization control could be achieved with the prepared initiators. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3858–3872, 2002     

Physical organic chemistry of supramolecular polymers

Unlike the case of traditional covalent polymers, the entanglements that determine properties of supramolecular polymers are defined by very specific, intermolecular interactions. Recent work using modular molecular platforms to probe the mechanisms underlying mechanical response of supramolecular polymers is reviewed. The contributions of supramolecular kinetics, thermodynamics, and conformational flexibility to supramolecular polymer properties in solutions of discrete polymers, in networks, and at interfaces, are described. Molecule-to-material relationships are established through methods reminiscent of classic physical organic chemistry.     

Electron transporting semiconducting polymers in organic electronics

Significant progress has been achieved in the preparation of semiconducting polymers over the past two decades, and successful commercial devices based on them are slowly beginning to enter the market. However, most of the conjugated polymers are hole transporting, or p-type, semiconductors that have seen a dramatic rise in performance over the last decade. Much less attention has been devoted to electron transporting, or n-type, materials that have lagged behind their p-type counterparts. Organic electron transporting materials are essential for the fabrication of organic p-n junctions, organic photovoltaic cells (OPVs), n-channel organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs) and complementary logic circuits. In this critical review we focus upon recent developments in several classes of electron transporting semiconducting polymers used in OLEDs, OFETs and OPVs, and survey and analyze what is currently known concerning electron transporting semiconductor architecture, electronic structure, and device performance relationships (87 references).     

Analysis of diverse direct arylation polymerization (DArP) conditions toward the efficient synthesis of polymers converging with stille polymers in organic solar cells

Despite the emergence of direct arylation polymerization (DArP) as an alternative method to traditional cross‐coupling routes like Stille polymerization, the exploration of DArP polymers in practical applications like polymer solar cells (PSCs) is limited. DArP polymers tend to have a reputation for being marginally inferior to Stille counterparts due to the increased presence of defects that result from unwanted side reactions in direct arylation, such as unselective C‐H bond activation and homocoupling. We report ten DArP protocols across the three major classes of DArP to generate poly[(2,5‐bis(2‐hexyldecyloxy)phenylene)‐alt‐(4,7‐di(thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole)] (PPDTBT). Through evaluation of the method and resulting photophysical and electronic properties, we show not all DArP methods are suitable for generating device‐quality alternating copolymers. When DArP PPDTBT was synthesized in superheated THF with Cs₂CO₃, neodecanoic acid, and P(o‐anisyl)₃, it generated polymers of exceptional quality that performed comparably to Stille counterparts in both roll coated ITO‐free and spin‐coated ITO devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2907–2918     

Peptide-directed microstructure formation of polymers in organic media

Synthesis and peptide-guided self-assembly of an organo-soluble peptide-polymer conjugate, comprising a sequence-defined polypeptide and a poly(n-butyl acrylate), are described. The amino acid sequence of the peptide encodes a high tendency to adopt an antiparallel beta-sheet motif, and thus programs the formation of tapelike microstructures. Easy synthesis and controllable self-assembly is ensured by the incorporation of structure breaking switch defects into the peptide segment. This suppresses temporarily the aggregation tendency of the conjugate as shown by circular dichroism, infrared spectroscopy (FT-IR), and atomic force microscopy (AFM). A pH-controlled rearrangement in the switch segments restores the native peptide backbone, triggering the self-assembly process and leading to the formation of densely twisted tapelike microstructures as could be observed by AFM and transmission electron microscopy. The resulting helical superstructures, when deposited on a substrate, are 2.9 nm high, 10 nm wide, and up to 2.3 mum long. The helical pitch is about 37 nm, and the pitch angle is 48 degrees . The helical superstructures undergo defined entanglement to form superhelices, leading to the formation of soft, continuous organo-gels. A twisted two-dimensional core-shell tape is proposed as a structure model, in which the peptide segments form an antiparallel beta-sheet with a polymer shell.     

Design of functional polymers based on organic synthesis - novel polymerizations of allene and propargyl derivatives

This paper describes our recent work dealing with novel polymerization methods of allene and propargyl derivatives. By the radical, cationic, and living coordination polymerizations, polymers bearing exomethylene moieties in the side chain could be obtained. The polymers obtained could undergo the cationic crosslinking reaction. As step-growth polymerizations, spontaneous copolymerizations, polyadditions with dithiols, and coupling polymerizations using palladium catalyst are also described.