合成醋酸研究的新进展

介绍了由以下几种方法合成醋酸研究的新进展：（１）甲烷的直接碳基化；（２）从合成气一步制醋酸；（３）甲醇的气相羰基化；（４）只用甲醇为原料制醋酸和醋酸甲酯

多齿双亚胺双膦配位的钌络合物的制备和氢化性能

等摩尔的Ru(OAc)2(Ph3P)2和N,N'-双-[邻-(二苯基膦)苯亚甲基] 乙二胺(简称P2 N2 )在回流的二氯甲烷或甲苯中反应,分别生成两个新型四齿胺膦配位的钌络合物Ru(OAc)2 P2 N2·2H2O和反式-RuCl2P2N2·2H2O.对两个络合物进行了元素分析、IR和NMR表征.在氢压 1.0 至 8.0 MPa和反应温度 30至 150℃的范围内,研究了它们催化α,β-不饱和酸的氢化性能.结果表明,上述两个络合物是温和条件下氢化丙烯酸为丙酸的有效催化剂

Green Synthesis: an Emerging Frontier in Organic Synthesis

[中文文摘]绿色合成是有机合成化学面向新世纪的学科前沿。本文探讨绿色合成的目标及实现这一目标的一些可能途径。[英文文摘]Green synthesis is emerging as a new front ier in organic synthesis. The aim of green synthesis and eight possible approaches for achieving it are summarized

Asymmetric Transfer Hydrogenation of Ketones Catalyzed by Chiral Multidentate Aminophosphine Ligands/Iron Cluster

从廉价易得、绿色环保的铁簇合物Fe_3(CO)_(12)出发,开展了其与手性多齿胺膦配体(R,R,R,R)-PN_4H_6原位生成的催化体系在酮; 的不对称转移氢化中的应用研究.通过考察温度、添加剂等影响因素,探索最优的反应条件,并将其进一步应用于多种芳香酮的不对称转移氢化反应,得到高达96; % ee的对映选择性.As one of the most abundant metals on earth, iron is cheap and low toxicity. Herein we reported the asymmetric transfer hydrogenation of (ATH) ketones catalyzed by the system generated in situ from chiral multidentate aminophosphine ligand (R, R, R, R)-PN4H6 and Fe-3(CO)(12). The effects of temperature and additive on the ATH of propiophenone were examined. After optimizing the reaction conditions, we applied the catalytic system to the ATH of various aromatic ketones, obtaining the corresponding optical active alcohols with high enantioselectivities (up to 96% ee).National Natural Science Foundation of China [21173176, 21673190];; Fundamental Research Funds for the Central Universities [20720150040

手性环状P2N4-型配体/钴簇合物催化芳香酮的不对称氢化反应

近年来，设计开发新型高效的手性非贵金属催化剂已引起了人们的广泛关注。本研究从廉价易得的钴络合物出发，将其与新型手性胺膦配体原位形成的催化体系用于芳香酮的不对称氢化反应中，并考察了温度、氢气压力、添加剂用量等对催化反应的影响。结果表明，以氢气作为氢源，KOH存在的条件下，手性环状P2N4-型配体L5与钴簇合物Co4（CO）12原位形成的体系能有效催化多种芳香酮的不对称氢化反应，获得较高的转化率，相应产物手芳香醇的对映选择性最高可达90% ee（enantiomeric excess，对映体过量）

Analytical Control of Asymmetric Transfer Hydrogenation of Acetophenone using Chiral Capillary Gas Chromatography

手性毛细管气相色谱跟踪苯乙酮不对称催化氢化反应过程许翩翩阮源萍高景星（厦门大学化学系固体表面物理化学国家重点实验室物理化学研究所厦门361005）在开发研究芳香酮氢化反应的新型手性催化剂时，通常采用苯乙酮不对称催化氢化生成苯乙醇的反应效率来评价手性氢...This paper deals with the process analysis of asymmetric transfer hydrogenation of acetophenone by using Chiral capillary gas chromatography.The solvents, acetophenone and phenylethanol enantiomers were wellseparated on a Chrompack CPcyclodextrinβ236M19 column with FID detector.The racemic phenylethanol was determined and the relative content of the enantiomer was 50.1∶49.9(n=6).The chromatographic separation enable accurate determination of e.e.value and conversion(%) of acetophenone.The absolute configuration of the major enantiomer of phenylethanol was determined from the elution order.This method may be suitable for research in process of asymmetric transfer hydrogenation of arometic ketones.国家自然科学基

Highly Enantioselective Synthesis of Heteroaromatic Alcohols Catalyzed by Chiral Diaminodiphosphine-Ruthenium(II) Complexes

Chiral diaminodiphosphine-ruthenium(II) complexes were found to be excellent catalysts for the asymmetric transfer hydrogenation of heteroatomic ketones in propan-2-ol. In the presence of potassium hydroxide, the enantioselective reduction of heteroaromatic ketones procceded smoothly to give chiral alcohols with excellent enantiomeric excess (up to 97% ee) under mild conditions without reduction of the heterocycle.National Natural Science Foundation of China [20423002, 20703034]; Natural Science Foundation of Fujian Province of China [2008J0235]; State Key Laboratory of Physical Chemistry of Solid Surface

手性铁催化体系在不对称催化中的应用研究

本文介绍了手性铁催化体系在酮及亚胺的不对称还原、烯烃及硫醚的不对称氧化、不对称环加成、不对称环丙烷化以及不对称frIEdEl-CrAfTS烷基化等反应中的应用.国家自然科学基金(No.20423002;20703034);福建省自然科学基金(No.2008J0235

Synthesis,Characterization and Solid-State CD Spectra of the Chiral Bisferrocenyl Ligands

以甲酰基二茂铁(1)和手性1,2-二苯基乙二胺[(1R,2R)-1,2-二苯基乙二胺(2R),(1S,2S)-1,2-二苯基乙二胺(2S)]为原料,经缩合、还原和N-烷基化反应,制备了一对新型手性四齿双二茂铁基配体[N,N′-二(二茂铁基甲基)-N,N′-二(2-羟基丙基)-(1R,2R)-1,2-二苯基乙二胺(5R)和N,N′-二(二茂铁基甲基)-N,N′-二(2-羟基丙基)-(1S,2S)-1,2-二苯基乙二胺(5S)].用元素分析、红外(IR)、质子核磁共振(1HNMR)、紫外-可见(UV-Vis)、固体圆二色(CD)光谱等对手性产物(3R-5S)进行了表征.固体CD光谱研究表明,配体5R(或5S)的手性特征和4R(或4S)相似而与3R(或3S)却有一定差别.A pair of novel chiral tetradentate bisferrocenyl ligands [N,N'-bisferrocenylmethyl-N,N'-bis(2-hydroproxypyl)-(1R,2R)-1,2-diphenylethane-diamine(5R),N,N'-bisferrocenylmethyl-N,N'-bis(2-hydroxypropyl)-(1S,2S)-1,2-diphenylethane diamine(5S)] were synthesized from ferrocenylcarboxaldehyde(1)and chiral 1,2-diphenylethane-diamine(2R or 2S)followed by the reduction of the Schiff bases with NaBH4 and subsequent N-alkylation with 1,2-propyleneoxide.All the chiral products(3R-5S)were charactered by elemental analysis,infrared(IR),1H nuclear magnetic resonance(1H NMR),ultraviolet-visible(UV-Vis)and solid-state circular dichroism(CD)spectra.The solid-state CD spectra reveal that the chiral characteristics of 5R(or 5S)are quite similar with 4R(or 4S)and it is also notable that there are some differences between 5R(or 5S)and 3R(or 3S).国家自然科学基金(20373056);; 福建省自然科学基金(2005YZ1020);; 厦门大学科技创新项目(B类,XDKJCX20061027)资