非螯合型手性双膦在苯乙烯的不对称催化氢甲酰化中的应用

非螯合型手性双膦在苯乙烯的不对称催化氢甲酰化中的应用吕士杰，成克军，周宏英，郑燕，傅宏祥（中国科学院兰州化学物理研究所羰基合成和选择氧化国家重点实验室，兰州７３００００）黄梁仁（中国科学院福建物质结构研究所，福州３５０００２）关键词手性双膦，不对称氢...     

光学活性环氧化物的酶催化合成

光学活性环氧化物的酶催化合成①夏仕文尉迟力沈润南李树本②（中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室，兰州７３００００）关键词光学活性环氧化物酶催化不对称合成动力学拆分１前言光学活性环氧化物含有两个手性碳，通过选择性开环和官能团转换...     

不对称催化氢化制备（S）—（＋）—萘普生：Ⅱ.不对称氢化反应条件

不对称催化氢化制备（Ｓ）－（＋）－萘普生１）Ⅱ．不对称氢化反应条件赵培庆宫照阳（中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室兰州７３００００）关键词萘普生不对称催化氢化反应条件分类号Ｏ６４３．３２不对称催化是分子催化研究中的前沿领域之...     

庚烯羰化制醇的原位红外光谱表征

庚烯羰化制醇的原位红外光谱表征１）焦凤英胡庆云陈艳晶（济南大学实验中心济南２５０００２）牛建中殷元骐（中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室兰州７３００００关键词庚烯均相催化氢甲酰化原位红外光谱铑膦催化剂铑催化剂（以较强碱性的三...     

几种自制手性配体及其在不对称催化中的应用

几种自制手性配体及其在不对称催化中的应用吕士杰王来来（中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室兰州７３００００）关键词手性配体不对称羰基化不对称烷基化分类号０６４３．３２不对称催化的核心问题是手性催化剂的设计与合成．绝大多数手性催...     

VPO／SiO2催化剂的制备及性能研究

ＶＰＯ／ＳｉＯ２催化剂的制备及性能研究牛童王晓来１）索继栓（中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室兰州７３００００）关键词ＶＰＯ／ＳｉＯ２催化选择氧化正丁烷顺酐分类号Ｏ６４３．３２利用混浆钒磷混合氧化物催化剂催化正丁烷选择氧化制...     

NiO／TiO_2－SiO_2催化剂上甲烷与二氧化碳转化制合成气

ＮｉＯ／ＴｉＯ_２－ＳｉＯ_２催化剂上甲烷与二氧化碳转化制合成气邓存，路勇，丁雪加（中国科学院兰州化学物理研究所ＯＳＳＯ国家重点实验室，兰州７３００００）关键词甲烷，二氧化碳，合成气，负载型Ｎｉ催化剂己有报道表明［１～４］，Ａｌ２Ｏ３担载的Ｎｉ金属催化...     

担载型过渡金属催化剂上CH4＋C2H4→C3H8反应的初步研究

担载型过渡金属催化剂上ＣＨ４＋Ｃ２Ｈ４→Ｃ３Ｈ８反应的初步研究阎子峰薛锦珍沈师孔①王弘立（中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室，兰州７３００００）关键词甲烷同系化过渡金属催化剂乙烯１前言在均相催化体系中，甲烷与其它饱和烃类的反...     

铂（Ⅱ）－二－双－（二苯基膦）乙烷离子配合物的晶体结构及Pt（Ⅱ）－CN￣－键断裂

铂（Ⅱ）－二－双－（二苯基膦）乙烷离子配合物的晶体结构及Ｐｔ（Ⅱ）－ＣＮ￣－键断裂杨帆，吕士杰，傅宏祥（结构化学国家重点实验室，中国科学院福建物质结构研究所，福州３５０００２）（羰基合成与选择氧化国家重点实验室，中国科学院兰州化学物理研究所，７３００...     

CTAB/TX-100微乳液凝胶固定化脂肪酶的催化水解活性

以α-单硬脂酸甘油酯的水解反应为指示反应,初步研究了CTAB/TX-100微乳液凝胶（MBG）固定化脂肪酶的催化水解活性及其主要影响因素。结果表明,在水溶液中,CTAB/TX-100 MBG固定化脂肪酶能顺利地催化α-单硬脂酸甘油酯的水解反应,且反应后凝胶块仍能保持较好的机械强度。其催化水解活性在反应初期增加明显,随反...     

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.     

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.     

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.     

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.