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Carbonylation of Alkynes with Different Nucleophiles Catalyzed By Transition Metal Complexes

Wendi Guo , Ye Liu

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (4) : 512 -523.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (4) : 512-523 DOI: 10.7536/PC200636
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Carbonylation of Alkynes with Different Nucleophiles Catalyzed By Transition Metal Complexes
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Abstract

Carbonylation(such as hydroformylation, alkoxycarbonylation, hydroxycarbonylation, aminocarbonylation) provides an effective way to synthesize the high value-added carbonyl compounds such as aldehydes(/alcohols), carboxylic acids, carboxylate esters, amides etc., which is advantageous with high atom-economy, excellent selectivities, and mild conditions in comparison to the oxidation. The raw materials involved in carbonylation are comprised of alkenes, alkynes, halohydrocarbons, alcohols etc. Thereinto, with CO or CO-surrogates as carbonyl source, carbonylation of alkyne with different nucleophiles(such as water, alcohols, amines) over transition-metal catalysts, is one of the most attractive processes to produce the corresponding carbonyl compounds like carboxylic acids, carboxylate esters and amines with 100% atom-economy. The obtained carbonyl compounds are widely applied in the production of pharmaceuticals, foods, and cosmetics as well as organic synthesis like polymerization, Aldol condensation and Micheal addition. In this review, the research status on carbonylation of alkynes in recent decade, in terms of reaction types and carbonyl sources, are summarized and prospected.

Contents

1 Introduction

2 Alkoxycarbonylation of alkynes

3 Aminocarbonylation of alkynes

4 Hydroxycarbonylation of alkynes

5 Double carbonylation of alkynes

6 CO surrogates in carbonylation of alkynes

6.1 Formates as CO source

6.2 Formic acid as CO source

6.3 Metal-carbonyl compounds as CO source

7 Conclusion and outlook

Graphical abstract

Keywords

carbonylation / alkynes / transition metal complexes / nucleophiles

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Wendi Guo, Ye Liu. Carbonylation of Alkynes with Different Nucleophiles Catalyzed By Transition Metal Complexes. Progress in Chemistry, 2021, 33(4): 512-523 DOI:10.7536/PC200636

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1 Introduction

Transition metal-catalyzed carbonylation reactions have been developed rapidly since Reppe first reported the nickel catalyzed synthesis of acrylic acid from acetylene, CO and water in the 1930s[1]. Various carbonylation reactions with CO as carbonyl source and alkenes, alkynes, halohydrocarbons and alcohols as substrates have been realized one after another, which has become an important way to produce high value-added bulk chemical products, fine chemicals and pharmaceutical intermediates. In recent years, with the gradual deepening of research, the research results of efficient construction of carbonyl compounds by C — H bond activation/carbonylation reaction have emerged, and even become a powerful means to introduce carbonyl into chiral molecules[2,3]. For example, Xu's group prepared a series of chiral isoindolinones and isoquinolinones by palladium-catalyzed asymmetric C-H carbonylation[3]. On the other hand, in order to overcome the shortcomings of CO, such as high toxicity, flammability, explosiveness and inconvenience in storage and transportation, the development of new green carbonyl sources such as formic acid and formaldehyde has become a research hotspot in the field of carbonylation[4]. Therefore, transition-metal-catalyzed carbonylation has important research significance and broad application prospects.
Among many carbonylation reactions of different raw materials, the carbonylation of alkynes has increasingly become a research hotspot in academia and industry because of its 100% atom economy and the development trend of green chemistry, and remarkable progress has been made. Transition metal-catalyzed hydroformylation of alkynes with syngas (CO/H2) to α, β-unsaturated aldehydes is one of the earliest explored reactions in the field of alkyne carbonylation and one of the effective methods for industrial synthesis of aldehydes[5⇓~7]. In addition to hydroformylation, the carbonylation of alkynes also includes the reaction of alkynes with CO (or CO substitutes) and nucleophiles NuH (alcohols, amines, H2O, etc.) To directly form high-value-added carbonyl compounds such as α, β-unsaturated carboxylic acids and their derivatives (Scheme 1)[8]. Carbonylation reaction can be divided into the following types according to different nucleophiles: when the nucleophile is alcohol, it is called Alkoxycarbonylation; When the nucleophile is an organic amine, it is called Aminocarbonylation; When the nucleophile is a H2O, it is called Hydroxycarbonylation. In addition, alkynes, nucleophiles and two molecules of CO can react to form dicarbonyl compounds in a "one-pot" way, which is called Double carbonylation of alkynes.
For the carbonylation reaction, most of the current catalysts are VIII transition metals, such as Pd, Fe, Ru, Rh, Ir and so on[9]. Transition metal-catalyzed carbonylation of alkynes has a wide variety of systems. Although the catalysts, substrates and nucleophiles are different, the generally accepted reaction mechanism is shown in Scheme 2.
Taking alkyne as an example, the whole reaction starts with the formation of metal hydride active species: (I) the triple bond of C C C of alkyne coordinates with the M-H bond of metal hydride, and the coordination direction is the key factor determining the regioselectivity (linear/branched products) of the reaction; (II) further addition of that two to form a vinyl metal intermediate; (III) CO insertion followed by formation of an acyl metal intermediate; And (IV) attack that nucleophile to obtain the target product, and simultaneously regenerating the metal hydrogen active specie to enter the next catalytic cycle. Metal hydrides as the core driving force. It plays an important role in the whole reaction process and is generally formed by the reaction of metal complexes with Brønsted acid promoters (methane benzene sulfonic acid, p-toluene sulfonic acid, etc.).

2 Carbonylation and Esterification of Alkynes

Transition metal-catalyzed carbonylation of alkynes has become one of the effective ways to construct α, β-unsaturated esters due to its 100% atom economy and simple operation, which is widely used in the preparation of perfumes, spices, pharmaceutical intermediates and other chemical products.
Phosphine ligands are the most important and widely used ligands in transition-metal-catalyzed homogeneous reactions. The electronic and steric effects of phosphine ligands can be changed by reasonably designing or modifying the phosphine ligands, so that the catalytic activity and the reaction chemistry/regioselectivity can be effectively regulated. Therefore, the development of phosphine ligands with excellent catalytic activity is the key to the breakthrough of palladium-catalyzed carbonylation and esterification of alkynes, and is also the focus of attention of researchers. In 1993, Drent et al. Developed a homogeneous catalytic system composed of Pd(OAc)2,2-PyPPh2 and MeSO3H and successfully applied it to the carbonylation and esterification of propyne, realizing the efficient conversion of propyne to methyl methacrylate (MMA) (Scheme 3)[10]. The results showed that the selectivity of methyl methacrylate could reach 98. 9% under the CO pressure of 60 bar and the reaction temperature of 45 ℃. The authors believe that the ligand 2-PyPPh2 has a unique dual function: one is to regulate the electron cloud density of the metal center through the chelation of nitrogen and phosphorus atoms with palladium (Ⅱ), thus stabilizing the Pd metal center; The second is to act as a "proton messenger", that is, the uncoordinated nitrogen atom in another molecular ligand can act as a proton acceptor to capture and transfer hydrogen protons.
Based on this classical catalytic system, many researchers began to design and develop new nitrogen-containing phosphine ligands to further improve the activity of carbonylation and esterification. In 1998, Reetz's team assembled a series of phosphine ligands L1 ~ L3 containing pyrimidine groups and applied them to the carbonylation and esterification of alkynes (Scheme 4)[11]. The results showed that when Pd(OAc)2 was used as catalyst and L1 as ligand, the conversion of 1-hexyne was more than 97% and the TOF was up to 7000 h-1. When the ligands were replaced by L2 and L3, the conversion of 1-hexyne decreased in the following order: L1 (97%) > L2 (70%) > L3 (2%). The authors believe that the more pyrimidine groups in the phosphine ligand, the stronger the electron-withdrawing effect on the P atom, which will break the electronic balance between the metal and the ligand, and then inhibit the carbonylation of alkynes.
In 2001, Matteoli's research group designed and synthesized a new phosphine ligand L4 (Scheme 5) containing furan ring by using diphenyl-2-pyridylphosphine as a modification platform[12]. Under the CO pressure of 40 atm and the reaction temperature of 50 ℃, phenylacetylene was converted to the branched ester with a yield of 99. 2% by the catalytic system composed of Pd(OAc)2/L4/CH3SO3H. The reaction system has excellent regional selectivity.
In 2004, Green et al. Developed an OPN-type functionalized phosphine ligand L5 (Scheme 6)[13]. The L5 modified palladium catalyst has good catalytic effect on the carbonylation and esterification reaction of propyne. Compared with 2-PyPPh2, L5 can chelate with Pd metal center more stably, and does not need too many ligands to maintain catalytic activity. The only disadvantage of this system is that the reaction time is long and the reaction rate is low.
In 2017, Butterworth's team constructed a series of adamantane phosphine ligands containing pyridine groups and explored the influence of substituents on the pyridine ring on palladium-catalyzed carbonylation and esterification of alkynes (Scheme 7)[14]. The results showed that when the 6-position of the pyridine ring was connected with an electron-donating group —CH3, the catalytic activity of the ligand was the highest. However, when a strong electron-withdrawing group —CF3 is attached, the catalytic activity is greatly reduced. The conversion of phenylacetylene to α, β-unsaturated carboxylic acid esters was completed in 4. 5 H with a 95% selectivity for branched products over L6 modified palladium catalyst at CO 45 bar and 60 ℃. Ligand L6 also has the chelating effect and proton transfer function of bidentate P-N ligands.
In 2018, Li Yuehui's research group designed and developed a class of bidentate P-N chelating ligand L7 based on carbazole rigid skeleton by C-N coupling and C-P coupling with bromocarbazole as raw material, and found that it showed high activity and selectivity in carbonylation and esterification of various aliphatic or aromatic alkynes (yield 45% -96%, selectivity of branched ester 95.0% -99.9%)[15]. X-ray single crystal diffraction shows that the Pd(L)Cl2 complex has a tetrahedral configuration, the nitrogen and phosphorus atoms of the ligand L are chelated with the palladium metal center, and the two chloride ions are coordinated in a cis-form. This newly developed bifunctional ligand shows a stronger coordination effect with the palladium metal center compared to the classical 2-PyPPh2 ligand (Scheme 8).
In 2019, Liu Ye's team designed and synthesized a new ionic multidentate phosphine ligand L8, and successfully realized the carbonylation and esterification of alkynes with water as an auxiliary (Scheme 9)[16]. The results show that there are two potential P-Pd-P chelating modes for the ligand, which can form a stable complex with Pd. The strong electron-withdrawing effect of imidazolium makes it show strong π-electron accepting ability. In-situ Ftir characterization showed that water as a promoter was beneficial to the formation and stability of [Pd-H]+ active species in the PdCl2(MeCN)2-L8 catalytic system.
For the carbonylation and esterification of alkynes, the products of most reaction systems are mainly branched α, β-unsaturated esters, and only a few catalysts tend to catalyze alkynes to produce linear products preferentially, in which phosphine ligands play a key role in the regulation of regioselectivity. Inoue's research group published the research on the reaction of 1-octyne with CO and MeOH to produce linear α, β-unsaturated esters catalyzed by palladium catalyst modified by bidentate phosphine ligand dppf (Scheme 10)[17]. The phosphine ligand dppf has a rigid skeleton and a large bite angle, while 1-octyne has a long chain alkyl group with large steric hindrance. In order to reduce the steric hindrance, the addition of Pd — H with alkyne C C will preferentially form a linear vinyl palladium intermediate.
In 2010, the Cole-Hamilton research team found that under the reaction conditions of 80 ℃ and CO 30 bar, phenylacetylene was mainly converted into linear α, β-unsaturated ester — cinnamate with the regioselectivity of 99% by using Pd2(dba)3 as the catalyst, BDTBMB with large steric hindrance as the ligand and MsOH as the acid promoter (Figure 11)[18]. The mechanism shows that there is a steric induction effect during the coordination addition of the active species of the [Pd-H]+ with C C alkynes, and the linear vinyl palladium intermediate is dominant, which is the decisive factor for the linear regioselectivity of the reaction. In addition, the carbonylation and esterification of symmetric internal alkynes were carried out by using the Pd2(dba)3/BDTPMB/MsOH catalytic system.

3 Carbonylation and Amination of Alkynes

As an important chemical, α, β-unsaturated amides play an important role in the preparation of natural products and fine chemicals. Alpha, beta-unsaturated amides can be constructed in one step by alkynes with organic amines (aromatic/aliphatic amines) or inorganic ammonium (phosphonium ammonium salts).
El Ali's group has done a lot of detailed and in-depth work on the carbonylation and amination of alkynes with aromatic amines[19,20]. Using n-heptyne and aniline as template substrates and Pd(OAc)2 as catalyst, the team achieved effective regulation of regioselectivity by changing reaction conditions such as phosphine ligand, solvent, carbon monoxide pressure and temperature (Figure 12). When dppp was used as the ligand and p-TsOH was used as the acid promoter, under the conditions of 7 atm CO and 120 ℃, the products were mainly branched amides. When dppb was used as the ligand and no acid was added, the product was mainly linear amide at 120 ℃ and 20. 5 atm syngas CO/H2(1∶1). The two catalytic systems followed the palladium hydride mechanism, especially in the B experimental conditions, the participation of H2 was conducive to the formation of stable [Pd-H]+ active species.
Similarly, Alper's group found that branched or linear amides could be obtained in high yields by simply changing the ligands and additives (Scheme 13)[21]. When p-aminophenol was used as nucleophile and Pd(OAc)2/DTBPMB/B(OH)3/5-ClSA was used as catalyst, linear α, β-unsaturated amides were obtained in yields of 95% ~ 99%. When the Pd(OAc)2/DPPP/p-TsOH catalytic system is used, the branched α, β-unsaturated amide can be obtained in a yield of 95% -99%. The catalytic system has excellent chemical/regioselectivity, wide functional group compatibility and good substrate universality, and is suitable for carbonylation and esterification processes of various alkynes and aromatic amines.
Compared with aromatic amines, aliphatic amines with strong basicity tend to quench hydrogen protons, which greatly inhibits the formation of palladium hydrogen active species. Therefore, the carbonylation and amination reactions using aliphatic amines as nucleophiles are more challenging.
In 2006, Alper et al. Found that the palladium-catalyzed carbonylation and amination of alkynes with aliphatic amines could be successfully achieved using ionic liquid [Bmim]NTf2 as solvent (Scheme 14)[22]. Phenylacetylene can be efficiently converted to 2-substituted acrylamides under mild reaction conditions without any acid aid. The ionic liquid is not only used as a reaction medium, but also has an auxiliary effect, which is beneficial to the formation of the target amide. The authors point out that the weak coordination effect of the Tf2N- endows the [Bmim]NTf2 with stronger polarity, which is helpful to stabilize the palladium metal center. After five times of recycling, the catalytic system still maintained excellent catalytic activity.
In 2019, Liu Ye's research team also realized the carbonylation and amination of alkynes with various aliphatic amines using dppp modified palladium catalyst without additional acid additives, and obtained various branched amide products with high selectivity and yield (Figure 15)[23]. The authors point out that it is difficult for the active species of [Pd-H]+ to exist stably under such strong alkaline conditions, so the amido-palladium complex is the real active intermediate.
Aliphatic tertiary amines are generally not effective amine sources for carbonylamination reactions. However, through the C-N bond activation strategy, Huang Hanmin's team successfully realized the palladium-catalyzed carbonylation and amination of alkynes with tertiary amine as the amine source (Scheme 16)[24]. The results showed that the branched α, β-unsaturated amide could be obtained in 77% yield by the reaction of phenylacetylene with triethylamine using 5 mol%Pd(dcpf)Cl2 as catalyst, 1. 0 mmol di-tert-butyl peroxide (DTBP) as oxidant and additional 10 mol%NH4Cl at 120 ℃ and 20 atm CO. The catalytic system is suitable for the carbonylation and amination reactions of various alkynes and aliphatic tertiary amines. In addition, the authors introduced stilbene as a radical scavenger into the reaction system, and the yield of the target product decreased by only 12%, excluding the possibility of a radical mechanism.
Beller's team found that compared with the noble metal palladium catalyst, the cheap and environmentally friendly iron catalyst had better catalytic effect on the carbonylation and amination of alkynes and aliphatic amines (Fig. 17)[25]. Using Fe3CO12 as catalyst and L9 as ligand, phenylacetylene reacted with cyclohexylamine at 120 ℃ and 10 bar CO to give linear unsaturated amide in 77% yield. The reaction system has good substrate universality and is suitable for the carbonylation and amination reactions of alkynes and various aliphatic amines, and the only disadvantage is that excessive amine needs to be added. Li Yuehui's research group further improved the iron-catalyzed carbonylation and amination of alkynes, and found that zirconium fluoride (ZrF4) as an auxiliary catalyst was more conducive to the conversion of alkynes and aliphatic amines to linear unsaturated amides (Scheme 18)[26]. The results show that the ZrF4 can significantly affect the F … H — N hydrogen bond and effectively activate the Fe3(CO)12.
Primary amide compounds are widely used in bioactive molecules, drugs and organic functional materials. As a direct amine source of primary amides, NH3 has a pungent odor and is rarely used in carbonylation reactions. Inorganic ammonium salt has become an effective substitute for ammonia because of its clean, simple operation and safe storage and transportation.
In 2018, Huang Hanmin's research team found that using NH4Cl as amine source and palladium catalyst modified by DPEphos phosphine ligand can realize the carbonylation and amination of various aromatic and aliphatic alkynes, and obtain branched α, β-unsaturated amides with high selectivity, with yields of 46% -92% (Figure 19 a)[27]. The solvent NMP can capture the HCl released in the reaction and promote the carbonylation process. In the same year, Liu Ye's research group used NH4HCO3 as solid amine source, Pd(OAc)2 and bidentate phosphine ligand dppp as catalyst, under the conditions of reaction temperature of 120 ℃ and CO pressure of 1.0 MPa, phenylacetylene could be converted into branched unsaturated amide with 100% selectivity, and the yield was as high as 95% (Figure 19-b)[28]. Compared with other bidentate phosphine ligands, the natural bite angle of Dppp is 91 °, which ensures the stable coordination of Dppp with Pd metal center. In addition, the H2CO3 released by the decomposition of NH4HCO3 can act as a weak Brønsted acid promoter to promote the active species of [Pd-H]+ and accelerate the reaction process.

4 Hydrocarboxylation of alkynes

Acrylic acid and its derivatives are important bulk chemicals, which are widely used in the preparation of paints, leather, rubber and super absorbent polymers, and have a very broad application prospect in the fields of coatings, construction and so on[29]. Acrylic acid is usually produced by the partial oxidation of propylene, but this method has many disadvantages, such as using petroleum cracking product propylene as raw material, using dangerous oxidants and low selectivity[30]. Comparatively speaking, the construction of acrylic acid through the hydrocarboxylation of alkynes is more green and efficient. However, the hydrocarboxylation of alkynes is a challenging research topic due to the weak nucleophilicity of H2O and the difficulty in purification of the resulting carboxylic acids.
In 1939, Reppe first discovered the route of synthesizing acrylic acid from acetylene, CO and H2O catalyzed by Ni(CO)4, but the toxicity of Ni(CO)4 limited its application in industry[1]. In 2008, Wang's research group realized the hydrocarboxylation of acetylene with Ni(OAc)2·4H2O/CuBr2 bimetallic catalyst at 200 ℃ and CO pressure of 6. 0 MPa.The conversion of acetylene was 90% and the selectivity of acrylic acid was 90%[31]. Unfortunately, this catalytic system has many disadvantages, such as harsh reaction conditions and complex reaction system.
Compared with the above nickel catalyst systems, palladium catalysts can show good catalytic activity under mild conditions, and the development of efficient palladium catalyst systems suitable for hydrocarboxylation has become a research hotspot. In 2009, Wang's group achieved efficient conversion of acetylene to acrylic acid using a Pd(OAc)2/2-PyPPh2/TfOH catalytic system (Figure 20)[32]. Under the optimal reaction conditions, the conversion of acetylene was 85%, the selectivity of acrylic acid was 99%, and the TOF reached the 1011 h-1.
In 2010, Cole-Hamilton team found that PdCl2(MeCN)2/BDTBPMB/MsOH catalytic system could successfully realize the hydrocarboxylation of phenylacetylene, and the catalytic system had high selectivity for linear α, β-unsaturated carboxylic acids (Scheme 21)[18].
In 2011, Williams team found that the catalytic system constructed by Pd(OAc)2, water-soluble bidentate phosphine ligand BINAPS and Al(OTf)3 could realize the hydrocarboxylation of phenylacetylene in aqueous phase, and the selectivity of the target product 2-phenylacrylic acid reached 100% (Figure 22)[33]. However, the catalytic system can not be effectively recycled, which also exposes its potential weaknesses and limitations.
Palladium-catalyzed hydrocarboxylation of alkynes usually requires the addition of a Brønsted/Lewis acid promoter to promote the formation of [Pd-H]+ active species. Liu Ye's group designed and developed a "tertiary phosphine-quaternary phosphonium" water-oil amphiphilic trifunctional ligand (Scheme 23) with both P (Ⅲ) coordination group and [P(V)+]Lewis acidic center, which played a unique catalytic effect in palladium-catalyzed hydrocarboxylation of alkynes. Under optimized conditions, 68% -91% of various alkynes hydrocarboxylation products could be obtained without additional acid additives[34]. In situ Ftir characterization shows that the [P(V)+] group can activate the H2O, which is conducive to the formation of stable [Pd-H]+ active species. In addition, when [Bmim] NTf is used as the solvent, the catalyst still has excellent catalytic activity after being used for 6 times, which effectively solves the problem of recycling of the catalyst.

5 Double carbonylation of alkynes

The double carbonylation of alkynes is an important research direction of carbonylation reaction system. At present, this reaction mainly focuses on the construction of succinic esters or succinimides using alcohols or amines as nucleophiles.
In 2018, Beller's research team designed and synthesized a new bidentate phosphine ligand L11 containing bipyridine substituents for the first time, and its modified palladium complex can significantly catalyze the dicarbonylation esterification reaction of phenylacetylene, CO and methanol to directly synthesize succinic diester, with a selectivity of 99% (Figure 24)[35]. Kinetic studies and control experiments showed that the products of the first step of carbonylation and esterification were linear and branched α, β-unsaturated esters, which could be further converted to the target diesters under the catalytic system, and the branched esters had more advantages than the linear esters in the conversion process.
In 2018, Liu Ye's team prepared a new bifunctional ligand L12, which contains both tertiary phosphine groups coordinated to Pd metal centers and Brønsted acid —SO3H groups providing H+[36]. By constructing a PdCl2(MeCN)2-L12 catalytic system, the double carbonylation esterification reaction of alkynes was successfully realized, and a series of succinate derivatives (Scheme 25) were efficiently synthesized in yields of 35% -86%. The catalytic activity of the Pd catalyst system modified by the bifunctional ligand is superior to that of the physical mixed system of Xantphos and MeSO3H, and the catalytic effect of "1 + 1 > 2" is realized. The intramolecular hydrogen bond was found to be beneficial to the structural stability of the intermediate diacylpalladium (F) by DFT simulation. In addition, the ionic liquid [Bmim]NTf2 is used as a solvent to realize the recycling for six times.
Brønsted acid usually provides hydrogen protons for [Pd-H]+ active species in carbonylation reaction, but excessive Brønsted acid can easily lead to alkylation of phosphine ligands and even quench the active species. In order to effectively solve this problem, Liu Ye's research group constructed a PdCl2(MeCN)2/Xantphos-Al(OTf)3 bifunctional catalytic system with strong Lewis acid Al(OTf)3 instead of Brønsted acid, and prepared a series of succinate derivatives (yields of 36% -86%) by double carbonylation and esterification of alkynes (Figure 26)[37]. In this bifunctional catalytic system, the Pd/Xantphos complex catalyzes the activation of alkynes and CO, while the Al(OTf)3 can activate methanol through Lewis acid-base interaction, making it a more efficient hydrogen source for the active species of [Pd-H]+.
In addition to this palladium-catalyzed system, Chatani's group reported a special class of double carbonylation esterification reactions[38]. The authors synthesized a series of 1,4-dicarboxylic acid esters (Scheme 27) using internal alkynes and 2-pyridinemethanol as substrates under the catalysis of Rh4(CO)12. It was found that, unlike the palladium catalyzed system, the pyridine N atom in the substrate 2-pyridinemethanol could coordinate with the rhodium metal center to form an enone intermediate, which promoted the subsequent carbonylation process.
Succinimide is an important component in the synthesis of many natural products, pharmaceutical intermediates and pesticide compounds, and has a wide range of applications in the fields of chemistry, biology and material science[39,40]. It is an important method to synthesize succinimide compounds by double carbonylation and amination of alkynes.
In 2009, Beller's group first reported the double carbonylation and amination of 3-hexyne catalyzed by cheap metal Fe (Scheme 28)[41]. The results showed that 3,4-diethylsuccinimide could be obtained in 93% yield by the reaction of 3-hexyne with ammonia using 2 mol% [Fe3(CO)12] as catalyst at 120 ℃ and 20 bar CO. Unlike the traditional metal hydride mechanism, the cycloiron complex is the key intermediate of the catalytic system. The highlight of this system is that it uses cheap metal iron as catalyst, gets rid of the dependence on traditional precious metals, and does not need additional ligands, which is economical and efficient. However, the substrate is limited to ammonia, which limits the diversity of products. In 2015, Dyson's team realized the double carbonylation and amination of alkynes with various organic amines using Pd(xantphos)Cl2/p-TsOH catalytic system[42]. Less basic aromatic amines can be converted to imide products more efficiently than aliphatic amines (Scheme 29).
Although the above catalytic systems have achieved good catalytic results, there is a common problem, that is, they are only suitable for internal alkynes, and can not realize the double carbonylation and amination of terminal alkynes. In 2018, Beller's team used air as a green oxidant to prepare a series of imide compounds through palladium-catalyzed oxidative carbonylation (Scheme 30)[43]. The catalytic system does not need expensive ligands or additives and is economical and efficient; Has good functional group compatibility, wide substrate universality and excellent regioselectivity, and is suitable for the double carbonylation amination reaction of various internal alkynes or terminal alkynes and organic amines.

6 Carbonyl sources in alkyne carbonylation

The traditional carbonylation reaction usually uses CO gas as the direct carbonylation source, but the toxic and flammable characteristics of CO and the special requirements for high-pressure equipment limit its application in organic synthesis, and the inconvenience of transportation and storage is also a problem in large-scale industrial production. Therefore, the development of safe, non-toxic, environmentally friendly and convenient transportation and storage of CO substitutes has become a hot research topic in the field of carbonylation. In recent years, researchers have developed a variety of carbonylation reactions using metal carbonyls, N, N-dimethylformamide, chloroform, formic acid and formic acid esters as alternative carbonyl sources[44][45][46][47][24].

6.1 Using formate as carbonyl source

Formic acid ester compounds are common substitutes for CO In alkyne carbonylation and esterification reactions,and have the characteristics of stability and high efficiency.in 2003,Chang's group realized ruthenium catalyzed carbonylation and esterification of alkynes using 2-pyridyl methyl formate as a CO substitute through a chelation-assisted strategy(Scheme 31)[48]。 Under the catalysis of Ru3(CO)12,α,β-unsaturated esters were obtained in 42%~89%yields with good regioselectivity.The authors suggest that the substrate 2-pyridinyl-methyl formate not only acts as a substitute carbonyl source,but also has the coordination function of N ligand,and its N atom can coordinate with the Ru metal center to form a stable six-membered transition state complex,thus effectively inhibiting the decarbonylation process of the acyl hydride intermediate 。
In 2011,Tsuji's group reported the carbonylation and esterification of alkynes using phenyl formate as the carbonyl source(Scheme 32)[49]。 Under the optimized reaction conditions(Pd(OAc)25 mol%,Xantphos 10 mol%,100℃,24 h),diphenylacetylene can be efficiently converted to the target product E-unsaturated ester with a yield of up to 99%.The mechanism study shows that phenyl formate decomposes in situ to produce CO and phenol under the action of the catalyst,and the subsequent carbonylation and esterification reaction of alkynes takes place.It is noteworthy that the bidentate phosphine ligand Xantphos shows excellent catalytic performance in the conversion of phenyl formate and the carbonylation and esterification of alkynes.In addition,the use of phenyl formate is crucial to the smooth progress of the reaction,and alkyl formates such as butyl formate,2-phenylethyl formate,benzyl formate and the like are not converted under the catalytic system 。

6.2 Formic acid as carbonyl source

Formic acid,as a cheap,readily available,environmentally friendly and renewable C1 resource,can be produced either by oxidation of biomass or by catalytic hydrogenation of carbon dioxide.It is regarded as an ideal and environmentally friendly alternative carbonyl source and is widely used in the hydrocarboxylation of alkynes。
In 2015,Zhou Qilin's group first reported the hydrocarboxylation of alkynes with formic acid as the carbonyl source(Scheme 33)[50]。 The authors used[Pd2(dba)3]·CHCl3and Xantphos as catalysts,and added a catalytic amount of benzoic anhydride.The conversion number reached 350 at 100℃.In addition,the catalytic system is also suitable for the efficient hydrocarboxylation of other terminal alkynes or internal alkynes,and the yield can reach 56%-97% 。
in 2016,the team found that In addition to palladium catalysts,nickel catalysts were also suitable for hydrocarboxylation of formic acid as a carbonyl source(Scheme 34 a)[51]。 Under the catalysis of the nickel catalyst modified by the bidentate phosphine ligand 1,2-bis(tert-butylmethylphosphine)benzene,phenylacetylene can be efficiently converted into unsaturated carboxylic acid products,and the TON value can reach 7700,which is much higher than that of the previously reported palladium catalyst.Due to the advantages of high activity,high selectivity and low cost,this reaction has become an economical and efficient route for the synthesis of acrylic acid.In the same year,Fu Yao's group also published the research on the highly selective realization of nickel-catalyzed hydrocarboxylation of alkynes using HCOOH as carbonyl source(Fig.34b)[52]。

6.3 Using metal carbonyl compound as carbonyl sources

Molybdenum hexacarbonyl(Mo(CO)6)is a convenient solid source of carbonyl.In 2015,Babu's team used phenylacetylene and piperidine as template substrates,Mo(CO)6as catalyst and carbonyl source,and isobutyraldehyde as auxiliary catalyst to obtain branched amide(Scheme 35)with a yield of 83%[53]。 The authors point out that Mo(CO)6and piperidine can form a Mo(CO)4(pip)2complex,which is not only the active intermediate of the catalyst,but also can provide CO for the reaction.The catalytic system substrate has wide substrate universality and is suitable for the carbonylation amination reaction of various terminal alkynes and secondary aliphatic amines 。

7 Conclusion and prospect

The carbonylation of alkynes catalyzed by transition metals such as Pd, Fe and Ru has become one of the important green routes for the preparation of carboxylic acids and their derivatives. Up to now, researchers have developed a large number of catalytic systems with excellent catalytic activity, and efficiently realized the synthesis of carbonyl compounds by carbonylation and esterification of alkynes, hydrocarboxylation, carbonylation and amination, and double carbonylation.
At present, the carbonylation of alkynes mainly uses CO as the carbonylation source. In view of the problems of high toxicity, flammability and inconvenience of high pressure operation of CO, the use of liquid or solid CO substitutes with reproducibility and low toxicity has become an important research direction of alkyne carbonylation in recent years. At present, formic acid, formic acid esters, metal carbonyls and the like are suitable carbonyl sources for the alkyne carbonylation reaction to replace CO. However, the application scope of these CO substitutes is relatively single, and the requirements for the catalytic system are more stringent. Therefore, the cheap and abundant CO gas will still be the widely used carbonyl source in carbonylation reaction, especially in the industrial application process of carbonylation reaction, CO as a carbonyl source has an irreplaceable position. In addition, the production of carbonyl compounds from CO2 is in line with the development trend of green chemistry, but the application of CO2 in the field of alkyne carbonylation is still facing great challenges. Therefore, there is a lot of room for exploration in this research.

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Funding

the National Natural Science Foundation of China(21972045)

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