人参寡肽的合成

使用溶液和有机磷肽缩合试剂DEPBT合成了从人参中分离鉴定的三个寡肽,N,N'－双－(γ-谷氨酰甘氨酰)胱氨酸1,N,N'－双-γ－谷氨酰胱氨酰甘氨酸2,N-γ-谷氨酰胱氨酰-双-甘氨酸3,以及γ-谷氨酰甘氨酰半胱氨酸。4.产物经离子交换树脂柱或HPLC纯化,用质谱、核磁共振谱、氨基酸分析进行了验证。     

人参属植物中水溶性非蛋白氨基酸与寡肽的研究

从人参属植物水提取液中分离鉴定了若干具有生物活性的非蛋白氨基酸,如神经抑制性递质,γ－氨基丁酸（GABA）,神经兴奋毒素,β－N－草酰基－L－α,β－二氨基丙酸（β－N－ODAP）。首次从人参根的水提取液中分离纯化与鉴定了一组N－末端为从谷氨酸,并以其γ－羧基形成肽键为特征的七个寡肽;其结构为P－Ⅰ（氧化型谷胱甘肽,GSSG）P－Ⅱ（氧化型谷胱甘酰胺）,P－Ⅲ[N, N‘-双－（γ－谷氨酰甘氨酰）胱氨酸,IGSSG]与P－Ⅳ（N－γ－谷氨酰胱氨酰－双－甘氨酸）,P－Ⅴ-（N,N‘-双－γ－谷氨酰胱氨酰甘氨酸）,P－Ⅵ（γ-谷氨酰精氨酸）与P－Ⅶ（还原型谷胱甘肽）。化合物P－Ⅱ至P－Ⅴ与P－Ⅶ均与氧化型谷胱甘肽有关。P－Ⅱ至P－Ⅵ的结构均经化学合成确证。化 合物P－Ⅲ为未见报道的新生物活性肽,具有比化合物P－Ⅰ强的促睡眠活性。同时还讨论了β－N－ODAP与GABA以及其它化合物的生物活性。     

肽的研究——Ⅴ.新的带保护基牛胰岛素A链氨端五肽和九肽的合成

本文叙述带保护基的牛胰岛素A链氨端五肽Ⅰ(N-苄氧羰基甘氨酰-异亮氨酰-缬氨酰-γ-叔丁酯谷氨酰-谷氨酰胺酰肼基甲酸叔丁酯)及九肽Ⅱ(N-苄氧羰基甘氨酰-异亮氨酰-缬氨酰-谷氨酰-谷氨酰胺酰-S-苄基半胱氨酰-S-苄基半胱氨酰-丙氨酰-丝氨酰脐)的合成。Ⅰ是由已知三肽Ⅲ(N-苄氧羰基异亮氨酰-缬氨酰-γ-叔丁酯谷氨酸乙酯)经二种不同的合成步骤分别缩合而得,五肽Ⅰ经三氟乙酸脱去γ-叔丁基和N-叔丁氧羰基后与已知四肽Ⅷ(S-苄基半胱氨酰-S-苄基半胱氨酰-丙氨酰-O-乙酰丝氨酸甲酯溴氢酸盐)借迭氮法缩合而得九肽酯Ⅸ再经肼解而得九肽肼Ⅱ。合成的三肽、四肽、五肽和九肽的化学纯度曾经纸层析、纸电泳、元素分析及氨基酸组成分析证明,其光学纯度(除九肽Ⅱ和Ⅸ外)皆曾经亮氨酸氨肽酶水解及水解物的氨基酸组成测定证明为L型,九肽Ⅸ是由光学纯L型的肽Ⅰ与Ⅷ经迭氦法缩合而成,因此Ⅸ以及Ⅱ很可能为光学纯L型。     

肽的研究 Ⅳ.带保护基的牛胰岛素A链羧基末端十二肽及十六肽的合成

本文报告带保护基的牛胰岛素A链羧端的十二肽Ⅰ(N-苄氧羰基缬氨酰-S-苄基半胱氨酰-丝氨酰-亮氨酰-酪氨酰-谷氨酰胺酰-亮氨酰-γ-甲酯谷氨酰-天冬酰胺酰-酪氨酰-S-苄基半胱氨酰-天冬酰胺甲酯)和十六肽Ⅱ(N-苄氧羰基-S-苄基半胱氨酰-S-苄基半胱氨酰-丙氨酰-丝氨酰-缬氨酰-S-苄基半胱氨酰-丝氨酰-亮氨酰-酪氨酰-谷氨酰胺酰-亮氨酰-γ-甲酯谷氨酰-天冬酰胺酰-酪氨酰-S-苄基半胱氨酰-天冬酰胺甲酯)的合成. 肽Ⅰ和Ⅱ是由前文合成的带保护基的九肽Ⅳ(N-苄氧羰基亮氨酰-酪氨酰-谷氨酰胺酰-亮氨酰-γ-甲酶谷氨酰-天冬酰胺酰-酪氨酰-S-苄基半胱氨酰-天冬酰胺甲酯)经溴化氢-乙酸法脱去N-保护基后按迭氮化合物法分别与三肽酰肼Ⅴ(N-苄氧羰基缬氨酰-S-苄基半胱氨酰-丝氨酰肼)和七肽酰肼Ⅷ(N-苄氧羰基-S-苄基半胱氨酰-S-苄基半胱氮酰-丙氨酰-丝氨酰-缬氨酰-S-苄基半胱氨酰-丝氨酰肼)缩合而得. 肽Ⅰ和Ⅱ经元素分析及氨基酸组成分析证明为分析纯.由于它们是由光学纯L型的肽Ⅳ,Ⅴ,Ⅷ等经迭氮化合物法缩合而成,因此肽Ⅰ和Ⅱ很可能皆为光学纯L型.肽Ⅰ能被亮氨酸氨肽酶水解为相应的组成氨基酸而不留显著的茚三酮阳性的残肽.     

一种基于共保护策略合成谷胱甘肽的新方法

报道了一种采用谷氨酸席夫碱Ni(II)配合物共保护L-谷氨酸α-氨基和α-羧基合成谷胱甘肽(γ-L-谷氨酰-L-半胱氨酰-甘氨酸)的新方法. 首先由手性助剂——2-[N-(N’-苄基-脯氨酰)氨基]二苯甲酮(1)、六水合氯化镍和L-谷氨酸反应, 得到谷氨酸席夫碱Ni(II)配合物2, 产率为98%; 进而采用二异丙基碳二亚胺(DIC)/1-羟基-苯并三氮唑(HOBt)复合缩合剂法与S-苄基-L-半胱氨酸反应, 得到S-苄基-γ-L-谷氨酰-L-半胱氨酸席夫碱Ni(II)配合物3, 产率为90%; 接着同样采用DIC/HOBt复合缩合剂法与甘氨酸反应, 得到S-苄基-γ-L-谷氨酰-L-半胱氨酰-甘氨酸席夫碱Ni(II)配合物4, 产率为95%; 然后稀酸水解配合物4, 得到S-苄基-γ-L-谷氨酰-L-半胱氨酰-甘氨酸(5), 产率为70%; 最后采用甲酸铵催化转移氢化脱除S-苄基, 得到谷胱甘肽(6), 产率为87%. 中间产物和终产物的结构经由旋光, 1H NMR, 13C NMR和HRMS表征.     

肽的研究 Ⅰ.带保护基的胰岛素A鏈氨端五肽的合成

本文报告三种带不同保护基的胰岛素A键氨端五肽的合成。它们是N-苄氧羰基甘氨酰-异亮氨酰-缬氨酰-γ-甲酯-谷氨酰-谷氨酰胺(Ⅰ)、N-苄氧羰基甘氨酰-异亮氨酰-缬氨酰-γ-甲酯-谷氨酰-谷氨酰胺酰肼基甲酸叔丁酯(Ⅱ)和N-苄氧羰基甘氨酰-异亮氨酰-纈氨酰-谷氨酰-谷氨酰胺甲酯(Ⅲ)。五肽Ⅰ是由初次合成的N-苄氧羰基甘氨酰-异亮氨酰-纈氨酸(Ⅵ)与γ-甲酯-谷氨酰-谷氨酰胺(Ⅸ)经羧酸碳酸混合酸酐法,或Ⅵ的酰肼衍生物与Ⅸ经迭氮化物法缩合而成。五肽Ⅱ是由Ⅵ与γ-甲酯-谷氢酰-谷氨酰胺酰肼基甲酸叔丁酯(Ⅺ)经混合酸酐法合成。五肽Ⅲ则系用活化酯法由谷氨酰胺甲酯的氨端开始,逐步与相应的N-保护的氨基酸对硝基苯酯缩合、延伸而得。在用混合酸酐法合成五肽Ⅰ中,从反应混合物分离得N-苄氧羰基甘氯酰-异亮氨酰-D-纈氨酸(ⅩⅫ)。由ⅩⅫ与Ⅸ合成五肽Ⅰ的立体异构体,N-苄氧羰基甘氨酰-异亮氢酰-D-纈氨酰-γ-甲酯-谷氨酰一谷氨酰胺(ⅩⅩⅢ)。由N-苄氧羰基-γ-甲酯-谷氧酰-谷氨酰胺酰肼基甲酸叔丁酯(Ⅹ)经脱去酰肼上的保护基后,用迭氮法与S-苄基-半胱氨酰-S-苄基-半胱氨酸缩合而得N-苄氧羰基-γ-甲酯-谷氨酰-谷氨酰胺酰-S-苄基-半胱氨酰-S-苄基-半胱氨酸(四肽ⅩⅩⅤ)。五肽Ⅰ、Ⅱ、Ⅲ,四肽ⅩⅩⅤ及其主要的合成中间肽的光学纯度均经亮氨酸氨肽酶、胰羧肽酶法或旋光法检定。在五肽的酶水解的条件下有部分的谷氨酰胺和谷氨酸变为四氢吡咯酮-(5)-羧酸-(2),致使该二氨基酸的测定值偏低。     

肽的研究——Ⅱ.带保护基的胰岛素A鏈羧端九肽的合成

本文报告带保护基的胰島素A鏈羧端九肽Ⅰ(N-苄氧羰基亮氨酰-酪氨酰-谷氨酰胺酰-亮氨酰-γ-甲酯-谷氨酰-天冬酰胺酰-酪氨酰-S-苄基半胱氨酰-天冬酰胺甲酯)的合成。Ⅰ是由N-苄氧羰基亮氨酰-酪氨酰-谷氨酰胺酰-亮氨酸(四肽Ⅱ)和由N-苄氧羰基-γ-甲酯谷氨酰-天冬酰胺酰-酪氨酰-S-苄基牛胱氨酰-天冬酰胺甲酯(五肽Ⅲ)脫N-保护基所得氨端自由的五肽(Ⅲa)經二环己基碳二亚胺法縮合而成。四肽Ⅱ和五肽Ⅲ分別由二种不同方法合成。多肽Ⅰ,Ⅱ和Ⅲ皆經元素分析、紙层析、紙电泳、酶水解分析証明系純粹,均一的L-型。在合50％的二甲基亚碸的三(羥甲基)甲胺緩冲液中亮氨酸氨肽酶仍能将脫N-保护基的四肽与九肽完全水解为相应的氨基酸。     

羟基磺酸、氨基磺酸和磺酰肽的合成

具有四面体结构的磺酸衍生物可用于模拟酯键和酰胺键水解的过渡态，特别是 含有四面体结构磺酰胺键的磺酰肽作为天然肽的硫类似物，广泛用于作为酶抑制剂 以及用来诱导抗体酶的半抗原。综述了羟基磺酸、氨基磺酸和磺酰肽的合成。重点 介绍了消旋的和手性的α－和β－取代的β－氨基磺酸及其酰氯和亚磺酰氯，γ－ 氨基－α，β－不饱和磺酸及其酰氯的合成，以及由它们作为基元分子通过液相和 固相方法来合成α－和β－取代的β－磺酰肽、亚磺酰肽及乙烯磺酰肽。     

α－和β－K_7［SiW_9O_（37）Fe_3（H_2O）_3］·xH_2O的

本文报道了从三缺位杂多阴离子α－和β－ＳｉＷ９Ｏ合成α－和β－［ＳｉＷ９Ｏ３７Ｆｅ３（Ｈ２Ｏ）３］７－的钾盐的方法．ＦＡＢ－负离子质谱表明，阴离子在溶液中主要是以单体形式存在，二聚体微量．阴离子中的配位水分子在甲苯中可被ＳＣＮ等配体取代生成具有特征颜色的配离子．标题化合物具有催化ＰｈＩＯ（亚碘酰苯）环氧化反式－二苯乙烯、苯乙烯、环乙烯生成相应环氧化物的性质．     

硒半胱氨酸和硒胱氨酸的间接气相色谱测定──溴化氰－气相色谱法

将硒半胱氨酸（ＳｅＣｙｓＨ）甲基化，对硒胱氨酸（ＳｅＣｙｓ）需还原后再甲基化。它们生成的甲基硒半胱氨酸（ＣＨ＿３ＳｅＣｙｓＨ）能与溴化氰（ＣＮＢｒ）发生专一性反应，定量生成的硒氰酸甲酯（ＣＨ＿３ＳｅＮ）可用气相色谱法（ＧＣ）测定。此法简称ＣＮＢｒ－ＧＣ法，检测限４×１０￣（－８）克ＳｅＣｙｓ，准确度８９．５％，相对标准差１２．１％，非含硒氨基酸不干扰。此法适于样品中微量硒氨基酸（硒蛋氨酸ＳｅＭｅｔ，ＳｅＣｙｓＨ和Ｓｅｃｙｓ）的测定。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.