TOTAL SYNTHESIS OF 3α，4α－OXIDOAGAROFURAN AND （－）－3β，4α－DIHYDROXY－β－DIHYDROAGAROFURAN

ＴＯＴＡＬＳＹＮＴＨＥＳＩＳＯＦ３α，４α－ＯＸＩＤＯＡＧＡＲＯＦＵＲＡＮＡＮＤ（－）－３β，４α－ＤＩＨＹＤＲＯＸＹ－β－ＤＩＨＹＤＲＯＡＧＡＲＯＦＵＲＡＮＦａＪｕｎＮＡＮ；ＸｉｎＣＨＥＮ；ＺｈａｏＭｉｎｇＸＩＯＮＧ；ＴｏｎｇＳｈｕａｎｇＬＩ；Ｙｕ...     

α—一铌二钼十五钨磷杂多酸盐的合成和性质研究

合成了通式为α－Ｍ７－ｘＨｘ［Ｐ２Ｗ１５Ｍｏ２ＮｂＯ６２］．ｘＨ２Ｏ］Ｍ＝Ｋ＾＋，（ＣＨ３）４Ｎ＾＋，（Ｃ２Ｈ５）４Ｎ＾＋，（Ｃ４Ｎ９）４Ｎ＾＋］的４种盐。用ＩＲ，ＵＶ吸收光谱，极谱，１８３ＷＮＭＲ，ＸＰＳ和ＸＲＤ等方法对其进行了表征，确认三取代的位置在Ｄａｗｓｏｎ结构的同一“极位”。研究了取代Ｗ原子数目对１８３ＷＮＭＲ化学位移的影响，发现“极位”Ｗ原子的１８３ＷＮＭＲ化学位移平衡值与取代原子数目     

SYNTHESIS AND CHARACTERIZATION OF NOVEL FUNCTIONAL HOST COMPOUNDS 1．MONO－（6－ANILINO－β－CYCLODEXTRIN）

ＳＹＮＴＨＥＳＩＳＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦＮＯＶＥＬＦＵＮＣＴＩＯＮＡＬＨＯＳＴＣＯＭＰＯＵＮＤＳ１．ＭＯＮＯ－（６－ＡＮＩＬＩＮＯ－β－ＣＹＣＬＯＤＥＸＴＲＩＮ）￥ＹｕＬＩＵ；ＹｉＭｉｎＺＲＡＮＧ；ＹｕｎＴｉＣＨＥＮ（Ｄｅｐａｒｔ...     

水溶性铑膦配合物HRh(CO)(TPPTS)_3及其相关体系的~1H-NMR研究

在液体高分辨ＮＭＲ谱仪上, 测定并比较了具有高效烯烃氢甲酰化活性的水溶性铑膦配合物ＨＲｈ（ＣＯ）（ＴＰＰＴＳ）３ 及与此有关的配体ＴＰＰＴＳ和ＯＴＰＰＴＳ分别在Ｄ２Ｏ、混合溶剂Ｄ２Ｏ－ＴＨＦ（ｄ８）－ＣＤ３ＯＤ中的１Ｈ－ＮＭＲ谱图, 并借助１Ｈ－１Ｈ ＣＯＳＹ谱对上述３ 种化合物的１Ｈ－ＮＭＲ谱峰进行了指认; 讨论了影响化学位移和偶合常数的因素, 为水溶性铑膦配合物催化剂的结构与催化性能的关联及新催化剂设计研究提供了基础数据．     

RESOLUTION OF DL－α－AMINO ACIDS ON A L－HYDROXY PROLINE CHIRAL PHASE BY LIGAND－EXCHANGE CHROMATOGRAPHY

ＲＥＳＯＬＵＴＩＯＮＯＦＤＬ－α－ＡＭＩＮＯＡＣＩＤＳＯＮＡＬ－ＨＹＤＲＯＸＹＰＲＯＬＩＮＥＣＨＩＲＡＬＰＨＡＳＥＢＹＬＩＧＡＮＤ－ＥＸＣＨＡＮＧＥＣＨＲＯＭＡＴＯＧＲＡＰＨＹ￥ＴａｏＣＨＥＮ；ＴｉａｎＢａｏＨＵＡＮＧ（ＣｈｅｎｇｄｕＩｎｓｔｉｔｕｔ...     

2D-NMR归属1,1,1-Kestopentaose的^1H和^1^3C共振谱线

１,１,１－Ｋｅｓｔｏｐｅｎｔａｏｓｅ是菊粉（Ｉｎｕｌｉｎ）类中的一个葡果糖化合物（β－Ｄ－果糖－（２→１）－β－Ｄ－果糖（２→１）－β－Ｄ－果糖－（２→１）－α→Ｄ－葡萄糖）本文采用各种２Ｄ－ＮＭＲ技术,包括Ｈ－ＨＣＯＳＹＦ１－去偶Ｈ－ＨＣＯＳＹ ＨＭＱＣ和ＨＭＢＣ等,归属了它的Ｈ和Ｃ的谱线,并得到了有关质子间的偶合常数,为进一步分析其在溶液中的三维空间结构打下了基础。     

NMR STUDY ON THE CONFORMATION CHANGE IN THE AGGREGATION PROCESSES OF 1，3－DI（α－NAPHTHYL）PROPANE AND DI（α－NAPHTHYLMETHYL）ETHER

ＮＭＲＳＴＵＤＹＯＮＴＨＥＣＯＮＦＯＲＭＡＴＩＯＮＣＨＡＮＧＥＩＮＴＨＥＡＧＧＲＥＧＡＴＩＯＮＰＲＯＣＥＳＳＥＳＯＦ１，３－ＤＩ（α－ＮＡＰＨＴＨＹＬ）ＰＲＯＰＡＮＥＡＮＤＤＩ（α－ＮＡＰＨＴＨＹＬＭＥＴＨＹＬ）ＥＴＨＥＲ￥ＲｕｉＱｓｉｎｇＸＩＥ；Ｚ...     

芳氢与配位硫原子之间（sp^2C—H…S）的分子内氢键

化合物（Ｅｔ４Ｎ）２「Ｐｄ２（ｍｐ）２（Ｈｍｐ）２」９１）Ｈ２ｍｐ＝２－巯基苯酚）的＾１Ｈ ＮＭＲ谱中芳氢Ｈ１６的峰出现在δ８．７９处，与预测值相差１．７，这是由于Ｈ１６与配位硫Ｓ２原子之间存在弱相互作用，即新型的ｓｐ＾２Ｃ－Ｈ…Ｃ之间的氢键作用。     

STUDY ON IN SITU LASER-INDUCED FLUORESCENCE SPECTROELECTROCHEMISTRY OF α,β

ＳＴＵＤＹＯＮＩＮＳＩＴＵＬＡＳＥＲ－ＩＮＤＵＣＥＤＦＬＵＯＲＥＳＣＥＮＣＥＳＰＥＣＴＲＯＥＬＥＣＴＲＯＣＨＥＭＩＳＴＲＹＯＦα，β，γ，δ－ＴＥＴＲＡ（４－ＴＲＩＭＥＴＨＹＬＡＭＭＯＮＩＵＭＰＨＥＮＹＬ）ＰＯＲＰＨＹＲＩＮ￥ＱｉａｎｇＨＵ；ＪｉＭｉ...     

α－一铌二钼十五钨磷杂多酸盐的合成和性质研究

合成了通式为α－Ｍ＿（７－ｘ）Ｈ＿ｘ［Ｐ＿２Ｗ＿（１５）Ｍｏ＿２ＮｂＯ＿（６２）］·ｘＨ＿２Ｏ［Ｍ＝Ｋ~＋，（ＣＨ＿３）＿４Ｎ~＋，（Ｃ＿２Ｈ＿５）＿４Ｎ~＋，（Ｃ＿４Ｈ＿９）＿４Ｎ~＋］的４种盐．用ＩＲ、ＵＶ吸收光谱、极谱、~（１８３）ＷＮＭＲ、ＸＰＳ和ＸＲＤ等方法对其进行了表征，确认三取代的位置是在Ｄａｗｓｏｎ结构的同一“极位”．研究了取代Ｗ原子数目对~（１８３）ＷＮＭＲ化学位移的影响，发现“极位”Ｗ原子的~（１８３）ＷＮＭＲ化学位移平均值与取代原子数目呈线性关系．     

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.