cis-[(trans-1,2-双(氨甲基)环丁烷)(3-羟基-1,1-环丁烷二羧酸根)合铂(Ⅱ)]的合成和抗癌活性

通过对洛铂和卡铂的结构进行重组和优化,合成了一种新型洛铂衍生物cis-[(trans-1,2-双(氨甲基)环丁烷)(3-羟基-1,1-环丁烷二羧酸根)合铂(Ⅱ)],采用元素分析、红外光谱、质谱和核磁共振表征了其化学结构,并考察了此化合物的水溶性和稳定性。应用标准SRB法测试了目标化合物对人肺癌细胞株(NCI-H460、A549)、人乳腺癌细胞株(DU4475)、人白血病细胞株(Sup-B15)生长的抑制活性,评价了它对人肺癌细胞NCI-H460裸鼠移植瘤的治疗作用。结果表明:目标化合物水溶性好、稳定,对多种癌细胞的生长有明显的抑制活性,IC_(50)均小于10μmol·L~(-1)。更重要的是,其体内对人肺癌细胞NCI-H460裸鼠移植瘤的治疗效果明显,与洛铂相当。     

1R，3S-1，2，2-三甲基-1，3-环戊二胺为配体的铂(Ⅱ) 配合物的合成、表征和抗肿瘤活性

本文合成了9种含有由天然D(+)-樟脑衍生的1R，3S-1，2，2-三甲基-1，3-环戊二胺(A)为配体的铂(Ⅱ)配合物[Pt(Ⅱ)AX]{其中，X=(CH₂)₃C(COO^-)₂(1，1-环丁烷二羧酸根)，2CH₃OCH₂COO^-，2CH₃CH₂OCH₂COO^-，2CH₃(CH₂)₃OCH₂COO^-，[OCH(CH₃)COO]^2-(乳酸根)，(OCH₂COO)^2-(乙醇酸根)，2CH₃OCH₂CH₂OCH₂COO^-，2CH₃CH₂OCH₂CH₂OCH₂COO^-和2CH₃(CH₂)₃OCH₂CH₂OCH₂COO^-}。通过元素分析、热重分析、红外光谱、¹H核磁共振谱和电喷雾质谱等对配合物进行了表征。体外生物活性测试表明，部分配合物对A549人肺癌细胞和HCT-116人结肠癌细胞具有较强的抗肿瘤活性。     

2，3-吡啶二甲酸和1，4-二咪唑基丁烷构筑的Cd（Ⅱ）配合物的合成、晶体结构及荧光性质

合成了一个配位聚合物{[Cd（pdc）（bbi）]·2H₂O}_n（H₂pdc=2,3-吡啶二甲酸,bbi=1,4-二咪唑基丁烷）,利用元素分析、红外光谱和X-射线单晶衍射考察了配合物的结构。配合物中,Cd(Ⅱ)的配位数为5,每个Cd(Ⅱ)与1个吡啶二甲酸离子的1个羧基氧原子和吡啶氮原子,另1个吡啶二甲酸离子的1个羧基氧原子,以及2个1,4-二咪唑基丁烷的2个氮原子配位。吡啶二甲酸离子的配位方式可以表示为μ-（κ³N,O²：O³）,Cd(Ⅱ)与之连接形成一维骨架链[Cd（pdc）]_∞。配体1,4-二咪唑基丁烷采用了“Ω”和“S”两种构型,它们进一步与中心原子配位形成三维网络结构。配合物为三重穿插的金刚石型网络结构,拓扑学符号为6⁶。受光激发,该配合物在426nm处有一个发射峰。     

双[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH2)n[CO2Sn(CH2CMe2Ph)3]2(n=5, 6)的合成、结构、热稳定性及生物活性

氧化双[三(2-甲基-2-苯基)丙基]锡分别与庚二酸和辛二酸反应, 合成了2个双[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH₂)_n[CO₂Sn(CH₂CMe₂Ph)₃]₂[(n=5 (1), 6 (2)], 经IR、¹H和¹³C NMR、元素分析和X射线单晶衍射对化合物进行了表征。化合物属单斜晶系, 空间群为P2₁/c。锡原子均为畸型四面体构型, 化合物1以氢键作用形成一维链状结构, 化合物2以氢键和C-H…π作用形成二维网状结构。化合物1和2在340 ℃以下具有良好的热稳定性, 对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460均具有较好的体外抑制活性, 且具有一定的抑菌活性。     

双[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH2)n[CO2Sn(CH2CMe2Ph)3]2(n=5,6)的合成、结构、热稳定性及生物活性

氧化双[三(2-甲基-2-苯基)丙基]锡分别与庚二酸和辛二酸反应, 合成了2个双[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH₂)_n[CO₂Sn(CH₂CMe₂Ph)₃]₂[(n=5 (1), 6 (2)], 经IR、¹H和¹³C NMR、元素分析和X射线单晶衍射对化合物进行了表征。化合物属单斜晶系, 空间群为P2₁/c。锡原子均为畸型四面体构型, 化合物1以氢键作用形成一维链状结构, 化合物2以氢键和C-H…π作用形成二维网状结构。化合物1和2在340 ℃以下具有良好的热稳定性, 对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460均具有较好的体外抑制活性, 且具有一定的抑菌活性。     

含吡啶的大环席夫碱锰（Ⅱ）配合物：合成、表征及抗菌性质

在Mn（Ⅱ）模板作用下,2,6-diacetylpyridine（DAP）及合适链状胺化合物通过[1+1]环缩合反应,合成了3个大环席夫碱配合物,并进行了红外、元素分析、质谱及电导率等表征及研究。测得了配合物[MnL¹（CH₃CN）]（ClO₄）₂的晶体结构,中心离子呈现出稍微扭曲的五角锥配位构型。研究了配合物对S.aureus（ATCC6633）,B.cereus（ATCC7064）,C.xerosis（ATCC373）（gram-positive bacterial strains）,E.coli（PTCC10009）,K.pneuomoniae（MTCC109）,and P.vulgaris（lio）（gram-negative bacterial strains）的抗菌活性。结果显示[MnL³]（ClO₄）₂抗菌活性明显优于[MnL¹（CH₃CN）]（ClO₄）₂ and [MnL²]（ClO₄）₂。在25℃条件下0.1mol·L^-1 KCl溶液中,通过电位计量法测定了化合物的质子化常数。     

ErxYb1-x（TPB）3Bath（x=0，0.218，0.799，0.896，0.987，1）配合物的近红外发光性能

采用4,4,4-三氟-1-苯基-1,3-丁二酮（TPB）为第一配体,4,7-二苯基-1,10-菲咯啉（Bath）为第二配体,分别制备了配合物 Er（TPB）₃Bath和Yb（TPB）₃Bath,以及它们的混合配合物Er_xYb_1-x（TPB）₃Bath（x=0.218,0.799,0.896,0.987）,并对所制得配合物的发光性能进行了系统研究。研究结果表明,所有配合物均能发射所含稀土离子的近红外特征光,并且可以通过调节混合配合物中的 n_Er/n_Yb来调控Yb³⁺/Er³⁺之间的能量传递,进而提高Er³⁺离子在1530 nm处的发光。     

一个由4，4’-（丁烷-1，4-二氧基）-二苯甲酸和双咪唑配体构筑的三重穿插金属有机骨架化合物

采用水热法合成了1个二维缠结金属有机框架化合物[Cu（bbi）_0.5（boba）]_n（1）（bbi=1,1’-（1,4-丁烷基）-二（咪唑）;H₂boba=4,4’-（丁烷-1,4-二氧基）-二苯甲酸）,并通过元素分析、红外光谱和单晶X-射线衍射对其进行了结构表征。结构分析显示：化合物1是具有聚轮烷和聚锁烃结构特征的三重平行穿插网络。此外还研究了它的荧光和热稳定性。     

(1iR, 1iiR, 2iR, 2iiR)-Ni, Nii-(1,3-亚苯基双(亚甲基))环己烷-1,2-二胺作为配体的双核铂配合物的合成及其抗癌活性

以(1ⁱR,1ⁱⁱR,2ⁱR,2ⁱⁱR)-Nⁱ, Nⁱⁱ-(1,3-亚苯基双(亚甲基))环己烷-1,2-二胺(HL)作为配体,设计并合成了7种双核铂配合物,并利用IR,¹H NMR,¹³C NMR,ESI-MS和元素分析等进行了表征。通过MTT法测定目标双核铂配合物对人类HepG-2,A549,HCT-116和MCF-7四种癌细胞系的细胞毒性。结果表明,所有的化合物对HepG-2,A549和HCT-116细胞系均表现了良好的细胞毒活性,但对MCF-7细胞系均无活性。其中,以3-羟基环丁烷-1,1-二羧酸为离去基团的配合物P7对HepG-2和A549细胞系的活性优于卡铂,对HCT-116细胞系的活性接近于奥沙利铂。     

(1iR,1iiR,2iR,2iiR)-Ni,Nii-(1,3-亚苯基双(亚甲基))环己烷-1,2-二胺作为配体的双核铂配合物的合成及其抗癌活性

以(1ⁱR,1ⁱⁱR,2ⁱR,2ⁱⁱR)-Nⁱ,Nⁱⁱ-(1,3-亚苯基双(亚甲基))环己烷-1,2-二胺(HL)作为配体,设计并合成了7种双核铂配合物,并利用IR,¹H NMR,¹³C NMR,ESI-MS和元素分析等进行了表征。通过MTT法测定目标双核铂配合物对人类HepG-2,A549,HCT-116和MCF-7四种癌细胞系的细胞毒性。结果表明,所有的化合物对HepG-2,A549和HCT-116细胞系均表现了良好的细胞毒活性,但对MCF-7细胞系均无活性。其中,以3-羟基环丁烷-1,1-二羧酸为离去基团的配合物P7对HepG-2和A549细胞系的活性优于卡铂,对HCT-116细胞系的活性接近于奥沙利铂。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

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%).     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

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.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

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.