碳硼烷硼端衍生物的合成与表征

在路易斯酸催化下,碳硼烷分别与对氰基溴化苄、三苯基膦在甲苯溶液里回流,前者反应中,制备得碳硼烷的硼端与对氰基苄基中的亚甲基直接偶联的产物1,通过调整催化剂的含量,可以显著地提高含B-Cl键的产物2的产率;与三苯基膦的反应中,碳硼烷失去一个硼顶,并与三苯基膦中的P原子直接偶联,生成含B-P键的巢式碳硼烷衍生物3。对此两类化合物进行了核磁、质谱、红外及单晶衍射等表征。化合物1和2中均发现碳硼烷的CH与N形成CH…N氢键和CH…π的弱作用,其中化合物2中,还存在CH…Cl。在巢式化合物3中,发现碳硼烷的CH参与了罕见的CH…HC相互作用。这类反应成功合成了含有B-C、B-Cl、B-P键的碳硼烷衍生物。     

基于B-H键的活化对含B-C、B-Cl、B-P键的碳硼烷硼端衍生物的合成与表征

在路易斯酸催化下,碳硼烷分别与对氰基溴化苄、三苯基膦在甲苯溶液里回流,前者反应中,制备得碳硼烷的硼端与对氰基苄基中的亚甲基直接偶联的产物1,通过调整催化剂的含量,可以显著地提高含B-Cl键的产物2的产率;与三苯基膦的反应中,碳硼烷失去一个硼顶,并与三苯基膦中的P原子直接偶联,生成含B-P键的巢式碳硼烷衍生物3。对此两类化合物进行了核磁、质谱、红外及单晶衍射等表征。化合物1和2中均发现碳硼烷的CH与N形成CH…N氢键和CH…π的弱作用,其中化合物2中,还存在CH…Cl。在巢式化合物3中,发现碳硼烷的CH参与了罕见的CH…HC相互作用。这类反应成功合成了含有B-C、B-Cl、B-P键的碳硼烷衍生物。     

含碳硼烷膦氧配体镍、铱化合物的合成与表征

碳硼烷双膦配体L1分别与三苯基膦氯化镍(NiCl₂(PPh₃)₂)和1,5-环辛二烯氯化铱(IrCl(COD))在空气中反应生成含巢式碳硼烷膦氧配体的镍、铱化合物1和2。本文对此两个化合物进行了核磁、质谱、红外及单晶衍射等表征。化合物1中溶剂分子氯仿与主体结构存在着常见的Cl…H氢键作用和较少见的CH…π作用,化合物2是首例以膦氧配体形成的Ir(Ⅰ)配合物,同时由于金属的差别导致了碳硼烷双膦配体被氧化程度的不同形成了新颖的碳硼烷[P,O]和[O,O]配体。     

含碳硼烷膦氧配体镍、铱化合物的合成与表征

碳硼烷双膦配体L1分别与三苯基膦氯化镍(NiCl2(PPh3)2)和1,5-环辛二烯氯化铱(IrCl(COD))在空气中反应生成含巢式碳硼烷膦氧配体的镍、铱化合物1和2。本文对此两个化合物进行了核磁、质谱、红外及单晶衍射等表征。化合物1中溶剂分子氯仿与主体结构存在着常见的Cl…H氢键作用和较少见的CH…π作用,化合物2是首例以膦氧配体形成的Ir(Ⅰ)配合物,同时由于金属的差别导致了碳硼烷双膦配体被氧化程度的不同形成了新颖的碳硼烷[P,O]和[O,O]配体。     

碳硼烷和碳硼炔金属配合物中金属-碳键的化学性质

碳硼烷和碳硼炔金属配合物中的金属-碳键具有不同于经典金属-碳键的化学性质.一方面,二十面体碳硼烷独特的电子和空间效应使得碳硼烷金属配合物中的金属-碳键不参与和不饱和分子的反应 另一方面,在一定条件下具有大空间位阻的碳硼笼可以诱导某些碳-碳偶联反应.然而,碳硼炔金属配合物中的金属-碳键能与多种不饱和分子发生反应,其反应模式取决于中心金属离子的电子构型.本文简要总结了我们近期在这方面的研究进展.     

钯催化硼-碳和硼-杂原子键构建一锅法合成双官能团化邻-碳硼烷※

碳硼烷是由碳氢和硼氢顶点组成的笼状分子, 在医药、能源和材料等领域有着重要应用, 但目前在碳硼烷硼顶点引入杂原子取代基的方法还较为有限. 基于此, 本工作从3-碘-邻-碳硼烷出发, 通过钯催化烯基化、金属迁移及后续与杂原子亲核试剂的偶联反应, 一锅法构筑硼碳键和硼杂原子键, 成功实现了一系列新型3-烯基-4-胺基/烷氧基/烷(芳)硫基-邻-碳硼烷衍生物的合成.     

半夹芯式16电子化合物CpCo(S2C2B10H10)与重氮乙酸乙酯及联烯三元反应体系

半夹芯式碳硼烷16e金属有机化合物CpCo（S₂C₂B₁₀H₁₀）与重氮乙酸乙酯及联烯在室温下反应,生成化合物1和2。在化合物1和2中,一分子重氮乙酸乙酯与一分子联烯以头-头方式插入Co-B键之间使碳硼烷B（3）/（6）位发生B-H键活化生成B-C键,另有一分子重氮乙酸乙酯使Co-S断裂形成硫叶立德。分别采用红外、核磁、元素分析、质谱和单晶X射线衍射等表征方法对化合物1和2进行了结构表征。     

半夹芯16电子碳硼烷化合物Me4CpCoS2C2B10H10与二茂铁炔酮的反应性

邻位碳硼烷分别与正丁基锂、硫粉和Me₄CpCo(CO)I₂反应合成得到半夹芯16电子碳硼烷化合物Me₄CpCoS₂C₂B₁₀H₁₀ (1).1与二茂铁炔酮在二氯甲烷中反应得到产物{(Me₄CpCoS₂C₂B₁₀H₁₀)[FcC(O)CHCCHCC(O)Fc]} (2)(Fc=二茂铁基).2是一个1:2的加成产物,2个二茂铁炔酮分子以头-尾的方式加成到分子1中的1个Co-S键上.1和2分别用红外、核磁、元素分析、质谱和单晶X-射线衍射等表征方法进行了结构表征.     

半夹芯16电子碳硼烷化合物Me4CpCoS2C2B10H10与二茂铁炔酮的反应性

邻位碳硼烷分别与正丁基锂、硫粉和Me₄CpCo(CO)I₂反应合成得到半夹芯16电子碳硼烷化合物Me₄CpCoS₂C₂B₁₀H₁₀ (1)。1与二茂铁炔酮在二氯甲烷中反应得到产物{(Me₄CpCoS₂C₂B₁₀H₁₀)[FcC(O)CHCCHCC(O)Fc]} (2)(Fc=二茂铁基)。2是一个1:2的加成产物,2个二茂铁炔酮分子以头-尾的方式加成到分子1中的1个Co-S键上。1和2分别用红外、核磁、元素分析、质谱和单晶X-射线衍射等表征方法进行了结构表征。     

一个含呋喃环顺磁性碳硼烷衍生物的合成及其生成机理

半夹芯16e化合物CpCoS₂C₂B₁₀H₁₀（Cp：cyclopentadienyl）（1）与2-呋喃炔酮在物质的量比为1：1.5时反应分离得到1个顺磁性化合物CpCoS₂C₂B₁₀H₉（C₁₂H₁₀O₂）（2）。在化合物2的合成过程中,一分子1中的Cp环与另一分子1中的B（3）/B（6）位连接;同时,该Cp环与1个2-呋喃炔酮分子发生Diels-Alder反应,生成1个双环[2.2.1]-2-庚烯基结构单元。此外,呋喃炔酮分子中的末端炔基碳原子与原料1中的1个硫原子相连,从而使得产物2中的钴中心离子是个17e中心。化合物2用红外、核磁、元素分析,质谱和单晶X-射线衍射分析等方法进行了表征。晶体属三斜晶系,空间群P1,晶胞参数：a=0.96657（11）nm,b=1.54423（15）nm,c=1.75650（18）nm,α=114.0800（10）°,β=105.433（2）°,γ=98.6390（10）°。     

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.