三嗪树枝状1,4,5,8-萘酰亚胺化合物的合成和荧光性能

采用收敛法合成了3代内核为1,4,5,8-萘酰亚胺, 端基分别含8个和16个乙基的三嗪树枝状大分子, 产物经IR, 1H NMR, 13C NMR及元素分析表征. 实验结果表明, 该方法无需保护/脱保护, 反应条件温和, 收率非常高. 通过荧光光谱对其荧光特性进行了初步研究, 发现经过树枝状修饰后的产物具有更好的荧光性能, 且随着代数的增加, 树枝状产物的荧光强度不断增强.     

新型树枝状受阻胺光稳定剂的设计、合成及性能评价

以二胺类化合物、丙烯酸甲酯、1,2,2,6,6-五甲基哌啶醇为主要原料, 经Michael加成、酯交换反应合成了一系列分子中含四个哌啶胺结构的新型树枝状化合物. 目标产物结构经¹H NMR, ¹³C NMR分析进行了确认. 选取其中一种结构进行抗氧化及抗老化性能测试, 结果表明其抗氧化性能优于主流抗氧剂Irganox B215及受阻胺光稳定剂Tinuvin770, Chimassorb944, Tinuvin622, 其抗老化性能优于受阻胺光稳定剂Tinuvin770.     

甲基对硫磷-D6的合成

报道了一种合成甲基对硫磷-D₆的新方法。以三氯硫磷、氘代甲醇和对硝基苯酚为起始原料,经三次酯化反应合成了目标产物甲基对硫磷-D₆,总收率47.6%,其结构经¹H NMR、 ¹³C NMR、 ³¹P NMR和HR-MS(ESI)确证。     

四色荧光标记二硫键可逆终端的合成及在DNA合成测序中的应用

分别以5-碘-2'-脱氧尿苷、 5-碘-2'-脱氧胞苷、 7-去氮-7-碘-2'-脱氧腺苷及7-去氮-7-碘-2'-脱氧鸟苷为原料, 以二硫键为可裂解连接单元, 通过多步反应合成了四色荧光标记不同碱基的脱氧核糖核苷酸; 研究了该类荧光标记核苷酸作为可逆终端在DNA合成测序中的应用. 所得产物结构经¹H NMR, ³¹P NMR及HRMS表征, 并对其进行了DNA高通量测序的测试. 结果表明, 该类荧光标记核苷酸作为DNA合成测序的可逆终端能够满足高通量测序的生化反应要求, 具有较好的应用前景.     

去甲基构树宁B的合成

以1,3-二羟基苯和对羟基苯甲醛为起始原料,经赫氏酰化、羟基保护、克莱森 斯密特缩合及催化氢化反应首次合成天然产物去甲基构树宁B,总收率40.9%,其结构经¹H NMR, ¹³C NMR和HR-MS(ESI TOF)确证。     

吡啶基双苯并咪唑的合成及其荧光性能

以多聚磷酸(PPA)为催化剂和溶剂,氮气保护下,吡啶基芳香二酸与邻苯二胺经缩合反应合成了三个新的吡啶基双苯并咪唑化合物(2a~2c),其结构经¹H NMR, ¹³C NMR, FT-IR和元素分析表征。2a~2c的固体荧光发射波长分别为473 nm, 427 nm和453 nm。     

天然产物Luxenchalcone的全合成

以对羟基苯甲醛和2,4-二羟基苯乙酮为起始原料,经过甲氧甲基化、溴代、Ullmann反应、羟醛缩合和脱保护等反应,完成了天然产物双查尔酮Luxenchalcone的全合成,关键步骤为Ullmann反应,重要中间体和目标产物的化学结构经 ¹H NMR,¹³C NMR和ESI-MS等表征确认.     

温度敏感型树枝状大分子衍生物的合成及药物控制释放

通过加入偶联剂活化末端羧基基团进行酰胺化反应, 将得到的带有羧基末端基团的温敏性聚N-异丙基丙烯酰胺接枝到整代的树枝状大分子聚酰胺-胺(PAMAM)上, 制备了树枝状大分子衍生物PAMAM-g-PNIPAm, 通过FTIR和¹H NMR表征其结构, 通过GPC和¹H NMR测定其分子量, 从而验证了接枝产物的形成; 通过紫外-可见分光光度计测定其在不同pH值缓冲液中的低临界溶胀/溶解温度(LCST)值, 发现产物的LCST值受缓冲液pH值的影响很大, 接枝前后的LCST值也发生了变化. 选用难溶性药物吲哚美辛作为模型药物, 考察了树枝状大分子及其温度敏感性衍生物PAMAM-g-PNIPAm作为载体对药物的包载、增溶和不同温度环境下的释放行为. 结果表明, 树枝状大分子衍生物对吲哚美辛具有增溶和控制释放的性能, 在难溶性药物的控制释放领域具有广阔的应用前景.     

新型含苯并磷杂环戊二烯结构荧光分子的合成及性能

以三苯胺、咔唑为电子给体, 苯并磷杂环戊二烯氧化物为电子受体, 设计合成了一类新颖的D-A-D 型荧光分子, 其结构经¹H NMR, ¹³C NMR, ³¹P NMR, IR和MS确认。通过紫外可见吸收光谱和荧光光谱系统研究了不同给体和受体单元对荧光分子的紫外吸收、液体荧光、固体荧光、溶致变色及聚集诱导发光等光物理性能的影响。结果表明：合成的三种分子具有良好的液体和固体荧光性能;化合物TBN-EPIO具有显著的溶致变色效应, 在四氢呋喃-水二元溶剂体系中, 具有聚集诱导发光(AIE)效应。此外, 利用密度泛函理论计算了分子的几何构型及前线分子轨道电子云。      

β-L-2’-脱氧胞苷的合成

β-L-2’-脱氧胞苷为重要的医药中间体。以2’-脱氧-L-核糖和胞嘧啶为起始原料，通过甲苷化、酯化、氯代、水解脱保护基等步骤，以49.7%的收率合成了β-L-2’-脱氧胞苷，HPLC纯度达99.9%。产物结构经¹H NMR, ¹³C NMR和MS确证。      

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.     

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%).     

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.     

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.     

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 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.