铃木-宫浦羰化反应在合成二芳基甲酮中的应用

近年来,钯催化的芳基卤化物和芳基硼酸化合物的羰化偶联反应发展十分迅速。到目前为止,大量硼酸化合物、钯催化剂前体、配体和羰基源被用来合成二芳基甲酮,此类化合物在工业中间体、染料、药剂、天然产物等领域有着广泛的应用。本文从钯催化剂体系、转金属促进剂、羰基源及其应用方面综述了铃木-宫蒲（Suzuki-Miyaura or Suzuki）羰化反应的研究进展。钯催化剂体系从均相和非均相体系两方面介绍,其中均相催化体系包括钯催化剂前驱体、磷配体、氮杂卡宾配体的研究进展;非均相催化体系主要介绍了活性炭、石墨烯、官能化硅胶、四氧化三铁等载体多种固载钯催化剂的应用。特戊酸添加剂可改善转金属化过程,有效加速羰化偶联反应。经典的羰化Suzuki反应一般需要气体钢瓶提供压力较高的一氧化碳气体。尽管近期一些研究实现了常压一氧化碳气球作为羰基供给源,使用一氧化碳释放分子（CO-releasing molecule,CORM）替代剧毒危险的一氧化碳气体可实现更为安全绿色的羰化反应进程。在双管反应器中,有机CORM可控降解释放一氧化碳,为钯催化羰基偶联反应提供CO。在微波辐射下,过渡金属羰基化合物可为羰基化反应原位直接提供CO。     

过渡金属配合物催化炔烃和亲核试剂的羰化反应

羰化反应(氢甲酰化反应、羰化羧酸化反应、羰化酯化反应、羰化酰胺化反应等)是制备醛(/醇)、羧酸、羧酸酯、酰胺等高附加值含氧羰基化合物有效的途径,具有反应原子经济性高、目标羰基化合物选择性高、反应条件较氧化过程更温和可控的优势.羰化反应的原料包括烯烃、炔烃、卤代烃、醇等有机化合物.其中,在过渡金属催化剂作用下,炔烃与不同...     

钯催化羰化叔丁基醚类制备异戊酸酯的研究

钯催化羰化叔丁基醚类制备异戊酸酯的研究周宏英，傅宏祥，陈静，李红兵，吕士杰，汪汉卿（中国科学院兰州化学物理研究所，兰州７３００００）羰基化合成已发展成为精细化工业中占有重要地位的技术之一。人们对羰基化反应的研究大多集中在以烯烃为原料，制备醛和醇的反应...     

镍 钴 钯 铁2—（二苯基膦基）吡啶配合物的合成及其催化羰基化反应

众所周知,铑催化剂是醇类羰基化的有效催化剂,但是铑价格昂贵且对设备有腐蚀性,因此,寻找出对醇类羰基化催化活性好的非贵金属催化剂,对醇类羰化的工业化有十分重要的意义。 本文在温和条件下,合成了四种含有相同配体(Ph_2PPy)不同金属的有机配合物(金属基分别为Ni、Co、Pd、Fe),并探索了它们对乙醇羰基化反应的催化活性。     

非光气含氮化合物催化羰化研究进展

本文对近几年来非光气含氮化合物羰化合成氨基甲酸酯及二取代脲的方法进行了概述,主要包括使用钯、钌、铑、硒、金等催化体系以一氧化碳为羰化剂进行的催化氧化羰化和催化还原羰化反应过程,以及使用碱催化体系以二氧化碳和碳酸二甲酯等为羰化剂的反应过程和机理.     

PROMOTERS IN THE CATALYST SYSTEM FOR METHANOL CARBONYLATION TO METHYL FORMATE

在一个机械搅拌式反应器中，在反应温度为６０～９０℃，压力为３～６ＭＰａ条件下试验了几种不同类型的化合物作为甲醇催化羰化合成甲酸甲酯碱金属醇碱催化剂的助催化剂。结果发现，在甲醇羰化制甲酸甲酯反应中，是助催化剂的极性而不是碱性起着重要的作用。同时证明，强极性非质子型化合物对该羰化反应具有良好的助催效果，乙腈则是一个例外。     

常压下电化学催化羰化直接合成异氰酸酯

近 2 0多年来 ,异氰酸酯的非光气合成方法一直受到人们的关注 [1] .采用 CO与硝基化合物羰化直接合成相应的异氰酸酯在理论上完全可行 [2 ] ,但由于异氰酸酯本身在所采用的高温、高压反应条件下很不稳定 ,实际产率很低 ,CO在醇存在下与硝基化合物催化还原羰化 [3 ,4 ] ,或与有机胺在氧气存在下催化氧化羰化 [5,6] 生成相应的化学性质较稳定的氨基甲酸酯 ,再将氨基甲酸酯通过高温热裂解生成异氰酸酯[7,8] .该反应在高温、高压下进行 ,条件较苛刻 ,因此探索在较温和的条件下实现直接合成异氰酸酯的途径是目前该领域中很具有挑战性的研究课题…     

一种新颖的胺类氧化羰化制脲衍生物催化剂

脲衍生物是一类具有广泛用途的有机反应中间体和药物中间体 .传统的生产方法是利用胺类化合物与异氰酸酯或光气的反应来实现[1] .在这些反应中都涉及到剧毒的光气 ,并且反应中放出大量的腐蚀性气体氯化氢 .采用催化氧化羰化或者还原羰化含氮有机物的反应制取相应的脲 ,是一条对环境和经济方面非常有利的路线 .在以往的研究工作中 ,普遍使用的是钯、钌、铑等贵金属的大分子含氮配合物均相催化体系或以硫、硒为主要活性组分的催化剂[2～ 6] .前者 ,催化剂制备过程相对复杂 ,还需添加其它助催化剂 ,与反应体系分离困难且易流失 ;后者活性较低 ,…     

钯-离子液体/钛硅复合氧化物催化剂的合及在胺羰化中的应用

长期以来 ,工业上一直使用光气合成法生产异氰酸酯类化合物 ,极易造成环境污染和人员伤害 ,因此研究无光气且环境友好的新工艺已引起广泛关注 .就经济角度考虑 ,由硝基类化合物进行还原羰化[1～ 4 ] 或胺类化合物进行氧化羰化 [5～ 13] 制备异氰酸酯比较有利 ,但是存在金属配合物催化剂的还原失活等问题[14 ,15] .室温离子液体作为一种具有特殊催化性能和可调控溶解能力的新型溶剂和反应介质已用于有机反应中 [16 ] ,但将其作为反应介质的含氮化合物进行羰化研究尚未见报道 .本文将离子液体应用于以硅酸四乙酯 ( TEOS)和钛酸四丁酯 ( TBO…     

有机金催化胺氧化羰化制氨基甲酸酯

自Haruta等报道高分散担载金催化剂对CO有良好的低温水除活性以来,金催化剂的研究开发开始受到关注,各种提载型金催化剂在选择氧化、氮氧化物消除、选择加氢、甲烷完全氧化以及均相有机金配合物催化剂在醇醛缩合、烯烃羰化、锡烷的偶联等反应中均取得了相当好的效果,但与Pt和Pd等贵金属相比,金作为具有潜在多种催化能力的催化材料了解尚少。现在工业上主要使用胺类化合物与剧毒的光气反应制取异氰酸酯,该反应造成设备腐蚀和环境污染,因此用胺类化合物氧化羰化或硝基化合物的还原羰化合成氨基甲酸酯,然后热裂解制取相应的异氰酸酯得到广泛研究,过去主要以含氮配体配位的钯催化剂为代表的贵金属为催化剂催化羰化合成氨基甲酸酯,以有机金配合物作为含氮化合物羰化催化剂的研究则未见报道,本文首次将有机金配合物作为胺类化合物氧化羰化制取氨基甲酸酯的催化剂,取得了与钯催化剂相当的催化效果,反应如下：R（NH2）n CO O2 R^1OH[Au(PPh3)x]yZ／→／PPh3R(NHCO2R^1)n H2O R=Ar-,RCH2-;R^1=CH3-,CH3CH2-;n=1 or 2,x=1 or 2,y=1 or 2;Z=cl,NO3,S。     

环氧化合物羰基化反应研究新进展

通过催化的方法在有机化合物分子中引入羰基和其它基团而成为含氧化合物的羰基化反应,具有"原子经济性"反应的高选择性和对环境的友好性,可充分利用资源和保护环境,符合绿色化学发展趋势等优点,备受学术界及工业界青睐.综述了近年来羰基钴金属化合物催化的环氧化合物和一氧化碳羰基化反应研究的新进展,涉及的反应类型主要包括羰基化扩环、羰基化开环共聚以及羰基化开环,讨论了不同类型反应的相关机理,并展望了该领域的研究前景.     

Recent progress on catalytic Heck carbonylations using carbon monoxide surrogates

Ongoing efforts toward the development of carbon monoxide (CO) surrogates have changed the way in which carbonylative transformations are conducted. For synthesizing carboxylic acid derivatives, Heck carbonylation using CO surrogates in slight excess has become a more efficient and practical method than the conventional one using large excess of CO gas. To supply CO for the reaction, both in-situ and ex-situ methods has been considered. Herein, we summarize recent progress in catalytic Heck carbonylation using CO surrogates, including discussion of the mechanism for CO generation from recently developed CO surrogates.     

Copper‐Catalyzed Carbonylative Coupling of Cycloalkanes and Amides

Carbonylation reactions are a most powerful method for the synthesis of carbonyl‐containing compounds. However, most known carbonylation procedures still require noble‐metal catalysts and the use of activated compounds and good nucleophiles as substrates. Herein, we developed a copper‐catalyzed carbonylative transformation of cycloalkanes and amides. Imides were prepared in good yields by carbonylation of a C(sp³)?H bond of the cycloalkane with the amides acting as weak nucleophiles. Notably, this is the first report of copper‐catalyzed carbonylative C?H activation.     

杂环化合物的羰基化反应

综述了近40年来杂环化合物和一氧化碳在金属络合物催化下的羰基化反应,详细讨论了不同类型反应的有关机理,并展望了该领域的研究前景.     

Carbonylation of Difluoroalkyl Bromides Catalyzed by Palladium

Although important progress has been made in the fluoroalkylation reactions, the transition‐metal‐catalyzed carbonylative fluoroalkylation reaction remains challenging so far. Herein, we report the first example of a Pd‐catalyzed carbonylation of difluoroalkyl bromides with (hetero)arylboronic acids under one atmosphere pressure of CO. The reaction can also be extended to the aryl potassium trifluoroborate salts. The advantages of this protocol are synthetic simplicity, broad substrate scope, and excellent functional group compatibility. The resulting difluoroalkyl ketones can serve as versatile building blocks for the synthesis of various useful fluorinated compounds.     

Iminophosphine palladium catalysts for Suzuki carbonylative coupling reaction

Three iminophosphine ligands having soft phosphorus and hard nitrogen atoms and their Pd(II) complexes were synthesized and characterized using ¹H NMR, ¹³C NMR, ³¹P NMR and Fourier transform infrared spectroscopic techniques. Also, electrochemical properties of the iminophosphines and their Pd(II) complexes were investigated in acetonitrile–tetrabutylammonium perchlorate solution with cyclic and square wave voltammetry techniques. All Pd(II) complexes were evaluated as catalysts for carbonylative cross‐coupling reactions of aryl iodides with phenylboronic acid. The Suzuki carbonylation of aryl iodides at 80 °C under balloon pressure of carbon monoxide in the presence of K₂CO₃ as a base was examined, and good to high conversions and excellent selectivities were obtained.     

Catalytic Carbonylation and Carboxylation of Organosulfur Compounds via C−S Cleavage

Transition‐metal‐catalyzed carbonylation with CO gas occupies a privileged position in organic synthesis for the synthesis of carbonyl compounds. Although this attractive and useful chemistry has led many researchers to investigate carbonylative transformations of various organic (pseudo)halides, C?S‐cleaving carbonylation of organosulfur compounds has been fairly limited. Recently, a broad spectrum of C?S‐cleaving transformations has been emerging in the field of cross‐coupling. In light of the importance of carbonyl compounds as well as considerable advancement for employing organosulfur compounds as competent surrogates of (pseudo)halides, carbonylative transformations of C?S bonds should be of high value. This Minireview focuses on catalytic C?S carbonylation of organosulfur compounds with CO or its equivalents. In addition, reductive carboxylation of C?S bonds with CO₂ is described.     

Aryl Formate as Bifunctional Reagent: Applications in Palladium‐Catalyzed Carbonylative Coupling Reactions Using In Situ Generated CO

After decades of development, carbonylation reactions have become one of the most powerful tools in modern organic synthesis. However, the requirement of CO gas limits the applications of such reactions. Reported herein is a versatile and practical protocol for carbonylative reactions which rely on the cooperation of phenyl formate and nonaflate, and the generation of CO in situ. This protocol has a high functional‐group tolerance and could be applied in carbonylations with C, N, and, O nucleophiles. The corresponding amides, alkynones, furanones, and aryl benzoates were synthesized in good yields.     

A highly selective cobalt-catalyzed carbonylative cyclization of internal alkynes with carbon monoxide and organic thiols

Despite the fact that many transition-metal-catalyzed reactions of organosulfur compounds with internal alkynes are ineffective, cobalt carbonyl (Co₂(CO)₈) is an excellent catalyst for carbonylative cyclization of internal alkynes with carbon monoxide. When Co₂(CO)₈-catalyzed reactions of internal alkynes with organic thiols are conducted in acetonitrile under 4 MPa pressure of carbon monoxide, thiolative lactonization of internal alkynes successfully takes place with incorporation of two molecules of CO. This carbonylation provides a useful tool to prepare the corresponding α,β-unsaturated γ-thio-γ-lactones (butenolide derivatives) in good yields. In the cases of unsymmetrical alkynes, such as 2-octyne and 6-methyl-2-heptyne, the thiolative lactonization proceeds with moderate regioselectivity to give the butenolide derivatives on which the carbonyl group preferentially bonds to the less hindered acetylenic carbon. Mechanistic pathways about the present thiolative lactonization are also discussed.