一氧化碳参与不饱和烃类化合物羰基化反应的研究进展

不饱和烃类化合物的羰基化反应是指在过渡金属催化剂存在条件下, 将一氧化碳(CO)分子以羰基的形式插入到烯烃(或者炔烃)与不同的亲核试剂中, 合成更高附加值化学品的转化过程. 本文综合评述了羰基化反应合成高附加值化学品的重要性, 介绍了几种不同类型的羰基化反应(氢甲酰化反应、 氢酯化反应、 氢酰胺化反应和氢羧基化反应)在发展新型催化剂体系及高效合成目标产物方面的研究进展, 并对羰基化反应存在的问题及未来发展方向和趋势进行了展望.     

Direct Vapor Phase Carbonylation of Methanol over NiCl2/C Catalyst

IntroductionThe carbonylation of alcohols via homogenous catalysis is important in manufacturingacetic acid and higher carboxylic acids and their esters[1 ,2 ] . The main route to produce aceticacid is to make methanol carbonylated by means of the Monsanto and BP process in which ahomogeneous rhodium catalystis used.Although the homogeneous carbonylation ofmethanolis a highly selective process,itisaffected by the disadvantagesassociated with a highly corro-sive reaction medium due to the use …     

Catalytic double carbonylation of epoxides to succinic anhydrides: catalyst discovery, reaction scope, and mechanism

The first catalytic method for the efficient conversion of epoxides to succinic anhydrides via one-pot double carbonylation is reported. This reaction occurs in two stages: first, the epoxide is carbonylated to a beta-lactone, and then the beta-lactone is subsequently carbonylated to a succinic anhydride. This reaction is made possible by the bimetallic catalyst [(ClTPP)Al(THF)2]+[Co(CO)4]- (1; ClTPP = meso-tetra(4-chlorophenyl)porphyrinato; THF = tetrahydrofuran), which is highly active and selective for both epoxide and lactone carbonylation, and by the identification of a solvent that facilitates both stages. The catalysis is compatible with substituted epoxides having aliphatic, aromatic, alkene, ether, ester, alcohol, nitrile, and amide functional groups. Disubstituted and enantiomerically pure anhydrides are synthesized from epoxides with excellent retention of stereochemical purity. The mechanism of epoxide double carbonylation with 1 was investigated by in situ IR spectroscopy, which reveals that the two carbonylation stages are sequential and non-overlapping, such that epoxide carbonylation goes to completion before any of the intermediate beta-lactone is consumed. The rates of both epoxide and lactone carbonylation are independent of carbon monoxide pressure and are first-order in the concentration of 1. The stages differ in that the rate of epoxide carbonylation is independent of substrate concentration and first-order in donor solvent, whereas the rate of lactone carbonylation is first-order in lactone and inversely dependent on the concentration of donor solvent. The opposite solvent effects and substrate order for these two stages are rationalized in terms of different resting states and rate-determining steps for each carbonylation reaction.     

STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A BIDENTATE POLYMER BOUND CIS-DICARBONYLRHODIUM COMPLEX AS CATALYST

Copolymer of 2-vinylpyridine and vinylacetate coordinated with dicarbonylrhodiumused as a catalyst for carbonylation of methanol to acetic acid and anhydride has beenstudied. The structural characteristics of the copolymer ligand and complex, and the in-fluences of the reaction conditions on the carbonylation catalyzed by this polymer complexhave been investigated. In comparison with small molecule catalyst of Rh complex, thebidentate copolymer coordinated complex has better thermal stability. The reactionmechanism of the carbonylation reaction is also illustrated.     

KINETICS OF THE CARBONYLATION OF METHANOL IN A MECHANICALLY AGITATED REACTOR

lntroductionThclox"-tcmpcraturcs)nthcsisofmcthanolfroms}'nthcsisgasviamcth}'lformatcconsistsofcarbon}'IationofMc0Htomcth}'lformatc(McF)(bclox`l()O"C).andhydr0gcnol\'sisofMcF(bclot"2OO"C)totx"oMcOHasshox`nbclo`"fCH30H C0=HC0OCH;l(l)HC00CH3 2H2=2CH3OH(2)Wcrcfcrtothisasthctx"o-stcpmcthanoIs}nthesis.Thccarbonylationofmcthanolisahomogcncousl}'catal}'zcdrcactionusingalkalimctalmethoxidesascataIystsinthellquidphasc.Thct},picalrcactionconditionsarc60~90"Cand3.O~5.OMPa.Thercactionisanex…     

Acylation of five-membered N-heteroaromatic compounds by ruthenium carbonyl-catalyzed direct carbonylation at a C-H bond

The ruthenium-catalyzed carbonylation at the C-H bond of five-membered N-heteroaromatic compounds is described. The reaction of imidazoles with CO and olefins in toluene in the presence of a catalytic amount of Ru(3)(CO)(12) results in carbonylation of the C-H bond at the 4-position (adjacent to the sp(2)-nitrogen) of the imidazole ring to give acylated imidazoles in good to high yields. A wide range of olefins can be utilized in the carbonylation reaction, and a variety of functional groups are compatible under the reaction conditions. Other five-membered N-heteroaromatic compounds, such as pyrazoles, oxazoles, and thiazoles, can also be used for the carbonylation reaction, and in all cases, carbonylation takes place exclusively at a C-H bond alpha to the sp(2) nitrogen. The reactivity of the five-membered heterocycles corresponds to the pK(a) of the conjugate acid of these heterocycles. The higher the pK(a) of the substrate, the higher is the reactivity. This indicates that the pK(a) values are related to the ability of the nitrogen atom in the substrates to coordinate to a ruthenium center. The coordination of the substrates to the ruthenium center in the catalyst complex is a necessary prerequisite for the carbonylation to proceed.     

Palladium-Catalyzed Low Pressure Carbonylation of Allylic Alcohols by Catalytic Anhydride Activation

A direct carbonylation of allylic alcohols has been realized for the first time with high catalyst activity at low pressure of CO (10 bar). The procedure is described in detail for the carbonylation of E-nerolidol, an important step in a new BASF-route to (−)-ambrox. Key to high activities in the allylic alcohol carbonylation is the finding that catalytic amounts of carboxylic anhydride activate the substrate and are constantly regenerated with carbon monoxide under the reaction conditions. The identified reaction conditions are transferrable to other substrates as well.     

Pd(OAc)2-catalyzed carbonylation of amines

A phosphine-free catalytic system [Pd(OAc)2-Cu(OAc)2-air] induced a substrate-specific carbonylation of amines in boiling toluene under CO gas (1 atm). Symmetrical N,N'-dialkylureas were obtained by the carbonylation of primary amines. N,N,N'-Trialkylureas were selectively formed by addition of a secondary amine to the above reaction vessel. Secondary amines did not give tetraalkylureas. However, dialkylamines with a phenyl group on their alkyl chains, such as N-monoalkylated benzylic amine or phenethylamine derivatives, underwent a direct aromatic carbonylation to afford five- or six-membered benzolactams. In the carbonylation, the chelation effect or steric repulsion between Pd(II) and the meta-substituent in the ortho-palladation and the ring sizes of cyclopalladation products that were formed prior to carbonylation were found to generate good site selectivity and increase the reaction rate. In contrast, carbonylation of omega-arylalkylamines with a hydroxyl group gave neither ureas nor benzolactams but instead produced 1,3-oxazolidinones smoothly. Hydrochlorides of amines also underwent carbonylation to afford the corresponding amides under the conditions used. This procedure made it possible to prepare ureas of amino acid esters and N-alkylcarbamates in practical yields.     

Acyl-lithiation of olefins: formation of cyclopentenones from 1-lithio-butadienes and CO

[reaction: see text] Intramolecular acyl-lithiation of C=C double bonds proceeds following carbonylation of 1-lithio-1,3-dienes with CO to afford 2- or 3-cyclopentenone derivatives in good to excellent yields after hydrolysis. Addition of electrophiles to the carbonylation reaction mixtures affords various multiply substituted cyclopentenones.     

硒催化羰基化合成苯并噻唑-2-氨基甲酸酯

以非金属Se为催化剂,以CO替代剧毒光气及其复杂衍生物作羰基化试剂,以O2为氧化剂,经2-氨基苯并噻唑与醇发生"一锅法"的硒催化氧化羰基化反应,开辟了一条经济、绿色、简便、高效的合成苯并噻唑-2-氨基甲酸酯类化合物的新途径.研究了反应温度、压力、醇的用量及碱的种类等因素对生成苯并噻唑-2-氨基甲酸酯的影响,获得了实施该...     

Dimethylformamide as a carbon monoxide source in fast palladium-catalyzed aminocarbonylations of aryl bromides

Dimethylformamide (DMF) acts as an efficient source of carbon monoxide and dimethylamine in the palladium-catalyzed aminocarbonylation (Heck carbonylation) of p-tolyl bromide to provide the dimethylamide. Addition of amines to the reaction mixture in excess delivers the corresponding aryl amides in good yields. The amines employed, benzylamine, morpholine, and aniline, all constitute good reaction partners. The reaction proceeds smoothly with bromobenzene and more electron-rich aryl bromides, but electron-deficient aryl bromides fail to undergo aminocarbonylation. The reactions are conducted at 180-190 degrees C for 15-20 min with microwave heating in a reaction mixture containing imidazole and potassium tert-butoxide: the latter is required to promote decomposition of the DMF solvent at a suitable rate. The beneficial effects of controlled microwave irradiation as an energy source for the rapid heating of the carbonylation reaction mixture are demonstrated. The carbonylation procedure reported herein, which relies on the in situ generation of carbon monoxide, serves as a convenient alternative to other carbonylation methods and is particularly applicable to small-scale reactions where short reaction times are desired and the direct use of carbon monoxide gas is impractical.     

甲醇羰基化制醋酸铱基催化剂的研究

摘要 醋酸是一种重要的化工原料，甲醇羰基化是目前生产醋酸的主要方法， 铱基催化剂是最有发展前景的甲醇羰基化反应制备醋酸的催化剂。介绍了铱基催化 剂体系的催化机理、速度影响因素，并与铑基催化剂进行了比较．     

超临界二氧化碳介质中钯催化炔烃羰基化反应

研究了以超临界二氧化碳为反应介质实现改善钯催化炔烃羰基化反应绿色性的方法 .研究结果表明 :醇的用量、二氧化碳压力和反应温度等因素均对钯催化炔烃羰基化反应的化学选择性均有影响 ,即存在炔烃的羰基化反应与氧化偶合反应的竞争     

顺二羰基铑（Ⅰ）共聚物催化剂的合成,结构与催化甲醇羰基化反应性能的研究

我们曾报道一系列含有两种不同配位基团的高分子共聚物与四羰基二氯二铑形成的顺二羰基铑(Ⅰ)配合物。这些配合物在催化甲醇羰基化反应中显示出高催化活性和高稳定性。本文采用4-乙烯吡啶(Y)和丙烯酸甲酯(B)共聚物为配体,对其与四羰基二氯二铑形成的配合物(YBRh)进行了表征。对该系列配合物催化甲醇羰基化生成乙酸的性能进行了评价。     

Carbonylation of epoxides to substituted 3-hydroxy-delta-lactones

Substituted 3-hydroxy-delta-lactones (3HLs) are valuable intermediates in the synthesis of pharmaceuticals and other biologically active natural products. Herein we report the first example of the catalytic carbonylation of substituted homoglycidols to 3HLs using HCo(CO)4. Upon optimization of the catalyst and reaction conditions, a functionally diverse set of 3HLs was prepared. Mechanistic insight was gained by observation of the carbonylation reaction using in situ IR spectroscopy, and we propose a mechanism that is consistent with previously studied epoxide carbonylation systems.     

硒催化的乙二胺、乙醇胺和环胺的氧化羰基化反应

研究了以硒粉作催化剂,一氧化碳为羰基化试剂的乙二胺、乙醇胺和一些环胺的羰基化反应,考察了氧化剂对反应的影响。发现氧气是该反应较好的氧化剂,而没有氧化剂存在时,几乎没有羰基化反应发生。在硒／氧化剂体系存在下,乙二胺和乙醇胺这样一些分子内具有相邻两个亲基团物质的羰基化反应易趋向于分子内羰基化形成较为稳定的五元环产物,产率和选择性较高;而环胺如哌啶和吗啡啉的羰基化可生成相应的四取代脲产物。对反应机理进行     

Liquid phase carbonylation with solid catalyst Part 2. Carboxymethylation of bromobenzene with group VIII metals supported on active carbon

It was found that palladium supported on active carbon showed high catalytic activities and selectivities for the carbonylation of bromo- and iodobenzene to benzoic acid derivatives in the liquid phase. The carbonylation activity increased with the addition of water to the reaction solvent.     

丙二酸锂-铑配合物的结构及催化性能研究

本文采用丙二酸锂为配体，与四羰基二氯二铑形成双齿配位的顺二羰基铑配合物，研究表明，在催化甲醇羰基化制乙酸的反应中，该配合物显示出高的活性和选择性。     

硒催化羰基化合成1,3,4-噻二唑-2-氨基甲酸酯

以非金属硒作为催化剂,以CO替代剧毒光气作为羰基化试剂,以O₂作为氧化剂,通过2-氨基-1,3,4-噻二唑与醇以"一锅法"方式发生硒催化氧化羰基化反应,提出了一种成本低、原子经济性高、合成路线简短及环境相对友好的合成1,3,4-噻二唑-2-氨基甲酸酯类化合物的新方法.研究了反应温度、醇的用量、压力及碱的种类等对合成1,3,4-噻二唑-2-氨基甲酸酯的影响,在优化反应条件下,2-氨基-1,3,4-噻二唑可与一系列醇顺利发生羰基化反应,以45%~90%的收率得到1,3,4-噻二唑-2-氨基甲酸酯类化合物.     

Oxidative carbonylation reactions: organometallic compounds (R-M) or hydrocarbons (R-H) as nucleophiles

Oxidative carbonylation reactions have attracted broad interest from both academia and industry in recent years. Enormous efforts have gone into the syntheses of carbonate and urea derivatives through the oxidative carbonylation of alcohols and amines. Very recently, organometallic reagents (R-M) and hydrocarbons(R-H) were directly employed as nucleophiles to construct a C-C bond in oxidative carbonylation reactions. This Minireview summarizes this novel type of oxidative carbonylation reaction.