β—环糊精衍生的手性氧膦配体在烯烃不对称氢甲酰化反应中的应用

β－环糊精衍生的手性氧膦配体在烯烃不对称氢甲酰化反应中的应用徐小红周宏英陈静傅宏祥１）（中国科学院兰州化学物理研究所兰州７３００００）关键词β－环糊精手性膦配体不对称氢甲酰化铑催化剂分类号Ｏ６４３．３２糖是一类含有丰富的手性碳原子的天然化合物，一些单...     

手性膦配体及其不对称催化的研究进展

手性膦配体及其不对称催化的研究进展①徐小红吕士杰傅宏祥（中国科学院兰州化学物理研究所，兰州７３００００）关键词膦配体手性配体不对称催化１前言手性是宇宙间的普遍特性，在生命的产生和演变过程中，自然界往往对一种手性有所偏爱．如：自然界存在的糖为Ｄ构型，氨...     

手性二茂金属膦配体在不对称合成中的应用及新进展

手性二茂金属膦配体在不对称合成中的应用及新进展牟宗刚，吕士杰，周宏英，傅宏祥（中国科学院兰州化学物理研究所兰州７３００００）关键词二茂铁膦配体，烯丙基化合物，二茂钌膦配体，不对称合成，不对称催化，均相催化１前言众所周知，催化作用的研究已成为近代化学的...     

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...     

有机金属试剂对羰基化合物不对称催化烷基化反应新进展

有机金属试剂对羰基化合物不对称催化烷基化反应新进展吕士杰，姜茹，傅宏祥（中国科学院兰州化学物理研究所，兰州７３００００）１．前言手性是自然界的一个重要现象，手性化合物在医药、农药、化学及生物功能等众多方面具有很重要的作用。长期以来，得到高对映纯的化合...     

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...     

一种新的手性三齿膦配体的合成及其应用

自从１９６６年第一个不对称催化反应［１］问世以来，研究最为广泛、深入的是不对称催化氢化反应．由于手性配体是手性催化剂产生不对称诱导和控制的源泉，因此，人们对手性配体研究得较为深入，已经出现了上千种不同结构的手性膦配体，其中手性双膦配体较多，而三齿膦配...     

非螯合型手性双膦铑对脱氢苯丙氨酸的不对称催化加氢反应

报道从Ｄ－甘露醇出发合成手性双膦（２Ｓ，５Ｓ）－３，６－双（二苯膦）－１，４：３，６－双脱水－２，５－双去氧－Ｌ－艾杜醇，原位下ＢＤＰＩ与３种铑配合物作用生成手性非螯合型双膦铑催化剂，常压下对４种脱氢苯丙氨酸衍生物进行不对称催化化反主尖，对反应结果及ｅ．ｅ．值进行了讨论。     

多相不对称催化氢化的研究进展

多相不对称催化氢化的研究进展１）左晓斌刘汉范（中国科学院化学研究所北京１０００８０）关键词不对称氢化多相催化镍、铂催化剂分类号Ｏ６４３．３２手性是自然界的一个普遍现象．手性分子在生命体内有着举足轻重的地位．如常见的糖类为Ｄ构型，氨基酸为Ｌ构型，蛋白质...     

亮点介绍

<正>钯催化不对称碳氢键活化构建磷手性中心化合物Angew.Chem.Int.Ed.2015,54,6265~6269含磷手性中心化合物可被用来合成手性膦配体在不对称催化反应中应用,但通常其合成会涉及到拆分或手性柱分离等过程.中国科学院上海有机化学研究所段伟良等对二芳基磷酰溴代苯胺的分子内碳氢活化反应进行了探索,尝试构建含磷手性中心化合物.发现钯催化剂结合酒石酸衍生的亚膦酰胺配体,可以选择性地切断磷上一个芳基的     

A chiral [2]catenane self-assembled from meso-macrocycles of palladium(II)

Reaction of trans-[PdX2(SMe2)2](X = Cl or Br) with the chiral ligand LL = 1,1'-binaphthyl-2,2'-(NHC(= O)-3-C5H4N)2 gave the [2]catenane complexes trans-[{(PdX2)2(micro-LL)2}2], which are formed by self-assembly from 4 units each of trans-PdX2 and LL. The catenation is favored by the formation of multiple hydrogen bonds between the constituent macrocycles (4 x NHClPd, 2 x NHO double bond C). If the ligand LL is racemic, each macrocycle trans-[(PdX2)2(micro-LL)2] is formed in the meso form trans-[(PdX2)2(micro-R-LL)(micro-S-LL)] but the resulting [2]catenane is chiral as a direct result of the catenation step. This is the first time that this form of chiral [2]catenane has been observed. The enantiomers of the [2]catenane further self-assemble in the crystalline form, through secondary intermolecular PdX bonding, to form a racemic infinite supramolecular polymer of [2]catenanes.     

溴化钯或乙酰丙酮羰基铑/手性配体催化醛与乙酰胺的不对称酰胺羰化反应研究

采用溴化钯为催化剂前体,与非螯合型双齿膦配体L1(DPPFF)、联吡啶型双齿膦配体L2(P-PHOS)和二茂铁基手性双膦配体L3((S,Rp)-BPPF)制备络合物催化剂,以乙酰丙酮羰基铑为催化剂前体,与手性亚磷酸酯配体L4-L6制备络合物催化剂,将其分别应用于底物环己基甲醛或苯乙醛的不对称酰胺羰化反应中,研究结果表明...     

Diastereoselective synthesis of [1]rotaxanes via an active metal template strategy

Despite the impressive number of interlocked molecules described in the literature over the past 30 years, only a few stereoselective syntheses of mechanically chiral rotaxanes have been reported so far. In this study, we present the first diastereoselective synthesis of mechanically planar chiral [1]rotaxanes, that has been achieved using the active template Cu-mediated alkyne–azide cycloaddition reaction. This synthetic method has been applied to the preparation of a [1]rotaxane bearing a labile stopper that can then be substituted without disruption of the mechanical bond. This approach paves the way for the synthesis of a wide variety of mechanically planar chiral [1]rotaxanes, hence allowing the study of the properties and potential applications of this class of interlocked molecular architectures.

The first diastereoselective synthesis of mechanically planar chiral [1]rotaxanes has been achieved using the active template Cu-mediated alkyne–azide cycloaddition reaction.     

Resolution of seven-coordinate complexes

The crystal structures of [Pr(dbm)3H2O] (1), [Sm(dbm)3H2O] (2), and [Er(dbm)3H2O] (3) have been determined (dbm=dibenzoylmethane). They display seven-coordinate propeller-shaped molecules, which are chiral and crystallize as conglomerates in space group R3. Analysis of the crystal structures reveals supramolecular interactions, including formation of a quadruple helix, which explain how stereochemical information can be transferred between stacks of molecules. A method to quantify the ee in bulk samples of stereochemically labile compounds by using solid-state CD spectroscopy is described. Using this method, it has been shown that compounds 1-3 undergo total spontaneous resolution directly after synthesis, forming a microcrystalline reaction product that is essentially enantiopure. The resolution of bulk quantities of seven-coordinate complexes (without chiral or polydentate ligands) is thus reported for the first time. Because the crystallization starts without seeding, the overall preparation may be regarded as absolute asymmetric synthesis.     

Synthesis of a selenidostannate(IV), [Mn(tepa).Sn3Se7]n, demonstrating the transformation from achiral to chiral and dimeric to polymeric structure

Although a number of chalcogenostannates have been obtained by using [M(amine)m]n+ as the structure director, these materials with chiral metal complex ions are usually achiral because they are a racemic mix of chiral complex cations. A chiral selenidostannate, [Mn(tepa).Sn3Se7]n (1; tepa = tetraethylenepentamine), containing incorporated [Mn(tepa)]2+ units, is reported herein. The unique structure is just like a grapevine appended with chiral grapes. In the same reaction, a centrosymmetric compound, [Mn(tepa)]2(mu2-Sn2Se6) (2), in which the Sn2Se64- anion acts as a bridge coordinating to [Mn(tepa)]2+ cations, has also been obtained. This is a reaction-time-related process in which compound 2 transformed gradually to 1 after prolonging the reaction time. This phenomenon demonstrates a transformation from achiral to chiral and dimeric to polymeric selenidostannate.     

具有氢键假想孔道结构的[M(en)3][GeF6](M=Ni,Co)的合成与表征

描述了两个具有管状氢键假想孔道结构的化合物[Ni(en)3][GeF6][JLG-1(Ni)]和[Co(en)3].[GeF6][JLG-1(Co)].在这两个结构中,[GeF6]2-阴离子与手性金属配合物阳离子[M(en)3]2+(M=Ni,Co)通过F…N之间复杂的弱氢键相互作用,在沿着63螺旋轴方向形成六方蜂窝状排布的管状氢键假想孔道.结构研究发现,配对的[GeF6]2阴离子和手性[M(en)3]2+阳离子同属于D3点群,这是JLG-1(Ni)和JLG-1(Co)形成管状氢键假想孔道的关键.这一研究成果对设计合成氢键假想孔道体系具有一定的指导意义.     

Synthesis of New Phase-Transfer Catalysts and Their Application in Asymmetric Alkylation

Despite phase transfer catalysis (PTC) is an important and useful method in organic synthesis, asymmetric synthesis using chiral phase-transfer catalyst has not been well documented and limited number of chiral phase-transfer catalyst have been developed^[1].In 1989,O'Donnell published his pioneering work in the asymmetric synthesis of α-amino acids by enantioselective alkylation of a prochiral protected glycine derivative using chiral phase-transfer catalyst^[2]. Since then, several groups reported their improvements on enantioselectivity and applicability on this useful synthetic reaction^[3,4]. However, almost all of the chiral phase-transfer catalysts reported so far are the derivatives of cinchona^[5]. In this presentation, we wish to describe the design and synthesis of a new type of chiral phase-transfer catalyst based on the camphor and its application in asymmetric alkylation of tert-bntyl glycinate-benzophenone Schiff base.     

Chiral layered zincophosphate [d-Co(en)3]Zn3(H0.5PO4)2(HPO4)2 assembled about d-Co(en)(3)3+ complex cations

A new chiral layered zincophosphate [d-Co(en)3]Zn3(H(0.5)PO4)2(HPO4)2, designated ZnPO-CJ16, has been hydrothermally synthesized by using the optically pure chiral metal complex d-Co(en)3I3 as the template. It contains 4.6-net sheets which array in a helical fashion with an ABCDEF stacking sequence along the [001] direction. The chiral d-Co(en)3(3+) complex cations reside in the interlayer regions. Interestingly, there exist symmetrical O...H...O H-bonds between inorganic sheets, which results in a pseudo-three-dimensional open-framework structure stabilized by strong H-bonds. The crystal data are as follows: ZnPO-CJ16, [d-Co(en)3]Zn3(H(0.5)PO4)2(HPO4)2; M = 818.26; hexagonal; P6(5)22 (No. 179); a = 8.5832(12) A; c = 52.610(11) A; U = 3356.6(9) A(3); T = 293(2) K; Z = 6; R1 = 0.0415 (I > 2sigma(I)); wR2 = 0.1383 (all data); Flack parameter, 0.04(4).     

Preparation and evaluation of calix[4]arene-capped beta-cyclodextrin-bonded silica particles as chiral stationary phase for high-performance liquid chromatography

Calix[4]arene-capped [3-(2-O-beta-cyclodextrin)-2-hydroxypropoxy]propylsilyl-appended silica particles (C4CD-HPS), a new type of substituted beta-cyclodextrin-bonded chiral stationary phase (CSP) for high-performance liquid chromatography (HPLC), have been synthesized by treatment of bromoacetate-substituted [3-(2-O-beta-cyclodextrin)-2-hydroxypropoxy]propylsilyl-appended silica particles (BACD-HPS) with calix[4]arene oxyanions in anhydrous N-methyl-2-pyrrolidone. The synthetic stationary phase is characterized by means of elemental analysis. This new type of CSP has a chiral selector with two recognition sites: calix[4]arene and beta-cyclodextrin (beta-CD). The chromatographic behavior of C4CD-HPS was studied with several disubstituted benzenes and some chiral drug compounds under reversed-phase conditions. The results show that C4CD-HPS has excellent selectivity for the separation of aromatic positional isomers and enantiomers of chiral compounds due to the cooperative functioning of calix[4]arenes and beta-CDs.