树脂上的固相合成——(一)多肽、低聚核苷酸、寡糖的固相合成

综述了典型的固相合成法,及其在多肽、低聚核苷酸和寡糖合成中的应用。比较了固相合成法与传统的液相合成法之优缺点。介绍了固相合成法中常用的高分子载体;氨基、羧基、羟基、磷酸基等功能基的化学保护方法。介绍了1984年诺贝尔奖金获得者,固相合成创始人R.B.Merrifield在此领域中的成就。引用了1963～1986年的60篇文献。     

固载化试剂和催化剂及其在液相组合合成中的应用

固载化试剂、催化剂及清洁树脂在液相合成中的应用, 极大地方便了液相合成的后处理, 提高了工作效率, 为液相平行组合合成提供了基础. 重点综述了近年来固载化试剂和催化剂在液相组合合成及多步液相合成中应用进展情况.     

Merrifield树脂在固相有机合成中的应用研究进展

综述了Merrifield树脂在固相有机合成中的应用研究进展, 主要包括两个方面: (1)在合成Merrifield树脂上的不同连接体中的应用; (2)Merrifield树脂在有机合成反应中的应用.     

片呐醇的绿色合成

综述了近年来片呐醇绿色合成研究的新进展,主要包括微波、超声波、固相合成、电合成、光化学合成等新技术、新试剂在该反应中的应用.     

固相有机合成

综述了近年来固相有机合成中采用的连接分子和连接策略及固相合成在有机合成中的应用。     

片呐醇的绿色合成

综述了近年来片呐醇绿色合成研究的新进展,主要包括微波、超声波、固相合成、电合成、光化学合成等新技术、新试剂在该反应中的应用。     

片呐醇的绿色合成

综述了近年来片呐醇绿色合成研究的新进展,主要包括微波、超声波、固相合成、电合成、光化学合成等新技术、新试剂在该反应中的应用。     

Knoevenagel缩合反应研究的新进展

综述了近年来Knoevenagel缩合反应研究的新进展, 包括微波、超声波、固相合成、离子液体等新技术新试剂在该反应中的应用.     

有机改性纳米二氧化硅和介孔SBA-15并固载钌配合物的表征与催化加氢性质

过渡金属钌配合物在均相和异相催化中,如加氢和加氢脱硫等方面具有广泛的应用.本研究主要从有机烯烃改性纳米二氧化硅和介孔SBA-15着手,将所合成的含有机硅基团配体的钌配合物有效地固载在改性的可溶性纳米二氧化硅和介孔SBA-15的表面,改性后固载型催化剂在有机相中具有良好的分散性,形成一个均相化的异相催化分子固载中心,并探究了其在烯烃加氢中的催化效果.研究结果表明,有机硅基团改性后的固载型钌催化剂具有较高及较稳定的催化效率,即常规烯烃在0.1 MPa压力下的催化加氢转化率可达到70%,而且具有较好的多次循环使用的绿色催化效果,这在分子催化方面具有非常好的潜在应用前景.     

AgNbO3的水热合成和光催化性质表征

采用水热合成法制备了AgNbO3粉末,运用XRD(X-ray diffraction),SEM(Scanning Electron Microscope)和UV Vis DRS (diffuse reflectance spectroscopy)对其表征,在可见光照射下通过降解亚甲基蓝,来评估样品的光催化活性,实验结果表明,目标化合物与固相合成法制备的AgNbO3相比较具有明显较高的催化活性,水热法制备的产物在光催化方面拥有广阔的应用前景.     

固相有机合成中的连接基团

介绍了固相有机合成中的连接基团,特别是带有隔离单元的连接基团、无痕迹连接基团、安全拉手型连接基团和复合型连接基团的基本概念、发展近况以及它们的应用.     

Recent advances in analytical construct resins

The area of solid-phase synthesis has witnessed exponential growth in the last fifteen years, but difficulties associated with the monitoring and analysis of resin-bound reactions and products have been apparent due to a limited number of analytical methods available. With the substrate tethered to an insoluble support traditional chromatographic monitoring is only possible after cleavage. In order to address this 'analytical bottleneck' Geysen, in 1996 elaborated Merrifield's initial dual linker strategy by incorporating an encoding system between two in-line linkers. These analytical construct resins represented a new approach for both the quality control of solid-phase combinatorial libraries and for the development of new synthetic sequences on solid-support. This review will summarize the development and application of analytical construct resins focusing on recent applications of the technology.     

Preparation of fluorinated linkers: use of 19F NMR spectroscopy to establish conditions for solid-phase synthesis of pilicide libraries

Three fluorinated linkers which are analogues of linkers commonly used in solid-phase peptide synthesis have been prepared. One of the linkers was used in combination with gel-phase 19F NMR spectroscopy to develop conditions for solid-phase synthesis of two libraries of pilicides, i.e. compounds designed to inhibit assembly of adhesive pili in uropathogenic Escherichia coli. Attachment to and cleavage from the linker could be monitored based on the chemical shift of the fluorine atom of the linker. In addition, use of the linker as internal standard allowed quantification and optimization of reactions occurring further away from the linker when fluorinated building blocks were employed. Importantly, high-quality 19F NMR spectra were obtained for compounds linked to a TentaGel resin in a standard NMR tube using an ordinary NMR instrument.     

An acid-stable tert-butyldiarylsilyl (TBDAS) linker for solid-phase organic synthesis

[reaction: see text] A new, robust tert-butyldiarylsilyl (TBDAS) linker has been developed for solid-phase organic synthesis. This linker is stable to both protic and Lewis acidic reaction conditions, overcoming a significant limitation of previously reported silyl linkers. Solid-phase acetal deprotection, olefination, asymmetric allylation, and silyl protecting group deblocking reactions have been demonstrated with TBDAS-linked substrates.     

A Surprising Solid-Phase Effect: Development of a Recyclable “Traceless” Linker System for Reactions on Solid Support

Triazenes as “traceless” linkers for solid-phase synthesis have been utilized for the attachment of arenes to a solid support and yield the corresponding products after various organometallic reactions (Heck reaction and asymmetric dihydroxylation, see the reaction scheme) and cycloadditions (Diels–Alder reaction). The triazene linker is distinguished by its accessibility, thermal robustness, and capability to undergo regeneration.     

Design, synthesis, and validation of rigid linkers for bioactive peptides

Rigid linkers of variable length were synthesized and used to connect two NDP-α-MSH ligands. The linkers were incorporated by solid-phase synthesis. Biological evaluations indicate that there is virtually no effect of these linkers on ligand binding to the human melanocortin 4 receptor.     

Solid-phase synthesis of polyfunctional polylysine dendrons using aldehyde linkers

A straightforward method for the solid-phase synthesis of C-terminally modified polylysine dendrons has been developed by applying bisalkoxybenzaldehyde and trisalkoxybenzaldehyde linkers. The method has been used for the synthesis of polylysine dendrons with a variety of C-terminal ‘tail groups’ such as alkyl, propargyl, and dansyl to give dendrons in high crude purity. Furthermore, the method was successful for the synthesis of dendrons with multiple N-terminal pentapeptide groups together with C-terminal alkyl and propargyl tail groups. Finally, the method was shown to be well-suited for automated synthesis.     

Dual linker with a reference cleavage site for information rich analysis of polymer-supported transformations

Two dual linker systems with specific reference cleavage sites were designed and synthesized to accelerate and simplify development and optimization of reaction conditions for solid-phase synthesis. The dual linker allows simple evaluation of cleavage rate of polymer-supported compounds from the linker and, at the same time, ensures that all resin-bound components are cleaved from the solid support. The dual linker 4 was assembled from two Wang linkers connected by a three carbon spacer. The linker 9 was synthesized using the PAL and HMPB linkers.     

Solid-phase Pd-catalysed cross-coupling methods for the construction of π-conjugated peptide nanomaterials

We describe the development of two procedures for the synthesis of peptides that are embedded with a variety of π-conjugated semi-conducting oligomers. These procedures utilise solid-phase variants of classical palladium-catalysed cross-couplings commonly used to prepare π-conjugated oligomers. The resulting peptide–π–electron hybrids are soluble in aqueous media and self-assemble to produce 1D nanostructures, simultaneously forming networks of π-stacked conduits. The procedures have allowed for the inclusion of complex chromophores including mixed aryl units, ethynylene linkers and sexithiophenes where the latter peptide's nanostructures demonstrated substantial conductivity when employed as an active layer in a field-effect transistor.     

Synthetic procedure for N-fmoc amino acyl-N-sulfanylethylaniline linker as crypto-Peptide thioester precursor with application to native chemical ligation

N-Sulfanylethylanilide (SEAlide) peptides 1, obtainable using Fmoc-based solid-phase peptide synthesis (Fmoc SPPS), function as crypto-thioesters in native chemical ligation (NCL), yielding a wide variety of peptides/proteins. Their acylating potential with N-terminal cysteinyl peptides 2 can be tuned by the presence or absence of phosphate salts, leading to one-pot/multifragment ligation, operating under kinetically controlled conditions. SEAlide peptides have already been shown to be promising for use in protein synthesis; however, a widely applicable method for the synthesis of N-Fmoc amino acyl-N-sulfanylethylaniline linkers 4, required for the preparation of SEAlide peptides, is unavailable. The present study addresses the development of efficient condensation protocols of 20 naturally occurring amino acid derivatives to the N-sulfanylethylaniline linker 5. N-Fmoc amino acyl aniline linkers 4 of practical use in NCL chemistry, except in the case of the proline- or aspartic acid-containing linker, were successfully synthesized by coupling of POCl(3)- or SOCl(2)-activated Fmoc amino acid derivatives with sodium anilide species 6, without accompanying racemization and loss of side-chain protection. Furthermore, SEAlide peptides 7 possessing various C-terminal amino acids (Gly, His, Phe, Ala, Asn, Ser, Glu, and Val) were shown to be of practical use in NCL chemistry.