IntechOpen

Home > Books > Carboxylic Acid - Key Role in Life Sciences

Open access peer-reviewed chapter

Recent Advances in the Synthesis of Carboxylic Acid Esters

Written By

Kouichi Matsumoto, Rina Yanagi and Yohei Oe

Submitted: 04 June 2017 Reviewed: 26 January 2018 Published: 13 June 2018

DOI: 10.5772/intechopen.74543

Carboxylic Acid IntechOpen
Carboxylic Acid Key Role in Life Sciences Edited by Georgiana-Ileana Badea

From the Edited Volume

Carboxylic Acid - Key Role in Life Sciences

Edited by Georgiana Ileana Badea and Gabriel Lucian Radu

Book Details Order Print

Chapter metrics overview

3,312 Chapter Downloads

View Full Metrics
Advertisement

Abstract

In this chapter, recent advances in the synthesis of carboxylic acid esters are summarized based on the utilization of carboxylic acids as electrophiles or nucleophiles in reactions. Condensation reagents or catalysts connect the carboxylic acids with the alcohols to afford the corresponding esters, together with the formation of 1 equiv. of H2O, in which the carboxylic acids can be regarded as the electrophile. In contrast, the carboxylate ion intermediates derived from the carboxylic acids react with alkyl halides, carbocations, or their equivalents to produce the esters, in which the carboxylate ions from the carboxylic acids can be regarded as the nucleophile. This chapter mainly introduces the recent progress in this field of the formation of esters, based on the classification of the role of carboxylic acids in reactions.

Keywords

  • esterification
  • carboxylic acids
  • condensation reagents
  • catalysts
  • reaction media
  • reaction methods
  • SN2 reactions
  • electrochemistry
  • transition metal catalysts
  • addition reactions

1. Introduction

In organic chemistry, the development of the efficient synthesis of carboxylic acid esters using carboxylic acids is still one of central research topics, because the organic material compounds, drug molecules, and natural products often contain ester unit as the functional group [1, 2, 3]. As for the view point of the synthesis of esters, the corresponding carboxylic acids are usually utilized as the key starting material and play an important role [1, 2, 3].

So far, many kinds of synthetic methods for the esters from carboxylic acids are well recognized and utilized, but a lot of researchers still have studied to investigate the new methods or aspects, because the synthesis of esters is also important from the point of view of green chemistry and industry. In this chapter, recent advances in the synthesis of carboxylic acid esters are described. The reactions are classified into two categories, i.e., the reactions utilizing carboxylic acids as (1) electrophiles and (2) nucleophiles, in which the reactions are conducted by using various chemical reagents and catalysts as well as by using interesting reaction media and methods. Although many papers have appeared in this filed, we herein have introduced important and selected examples because of the limitation of number of pages.

Advertisement

2. Synthesis of carboxylic acid esters using carboxylic acids as electrophiles

The typical and traditional method for the synthesis of carboxylic acid esters is the reaction of carboxylic acids with an excess amount of alcohols in the presence of a catalytic amount of H2SO4 by using Dean-Stark apparatus [1, 2, 3], in which H2SO4 catalyzes the addition of the alcohol to the carboxylic acid, and the H2O thus generated is removed by Dean-Stark apparatus (Scheme 1 (a)). This reaction is called as Fischer esterification. However, there are some drawbacks. The excess amount of alcohols is used. The Dean-Stark apparatus is usually necessary. In addition, the substrates bearing the functional group which reacts with the acid cannot be utilized in this reaction. The alternative and reliable method to be developed is the use of DCC in the presence of a catalytic amount of DMAP (Scheme 1 (b)) [4]. DCC can serve as useful condensation reagents. The use of DCC as the condensation reagent realizes the decrease of the amount of alcohols. In addition, Mitsunobu reaction is also reliable method [5, 6, 7, 8].

Scheme 1.

Typical and traditional procedures for the synthesis of carboxylic acid esters and their chemical structures of reagents.

Besides the use of DCC, other condensation reagents are also developed. 2-Halo-pyridinium salts called Mukaiyama condensation reagent serve as effective reagents [9]. Mukaiyama et al. have extensively contributed this research area for the development of useful condensation reagents [10]. In addition, BOP ((benzotriazol-1-yloxy)-tris(dimethylamino)phosphonium hexafluorophosphate)) [11, 12], CDI (carbonyldiimidazole) [13, 14], DMT-MM (4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride) [15, 16, 17], and so on [18, 19] are well established and used in the ester formation reactions.

As described above, many condensation reagents have been developed so far. However, there are still reports for this filed. Table 1 shows recent and selected reports of condensation reactions between carboxylic acids and alcohols using a stoichiometric amount of condensation reagents. Basically, the amount of alcohols is not excess (Table 1). For examples, polymer-bounded Ph3P (or Ph3P)/I2/microwave [20, 21, 22, 23] and Ph3P/I2/Zn(OTf)2 condition [24] have been reported, because the combination of PPh3 and I2 in the presence of the base has been well known so far [25, 26]. In addition, the use of Ph2PCl/I2/imidazole [27], Ph3PBr2 [28], POCl3/DMAP/Et3N [29], or PPh3/BnN3/microwave (Staudinger’s phosphazene) [30] systems was found to be effective for the esterification. The hypervalent iodine reagents could be utilized in coupling reactions [31, 32]. The combination of PPh3 and trichloroisocyanuric acid was also effective [33]. These reactions are based on the activation of PPh3. The catalytic activation of PPh3 can be achieved by iron [34]. Photo-irradiated procedure in the presence of PPh3 with a catalytic amount of flavin and azo compound under O2 was developed [35]. XtalFluor-E and tropylium-based coupling reagents were found to be effective for the esterification [36, 37].

Table 1.

Various condensation reagents and conditions used for the synthesis of carboxylic acid esters under the nearly equimolar carboxylic acids and alcohols (recent and selected examples).

In the view point of green chemistry, the use of a catalytic amount of reagents is one of the attractive approaches, in which the ratio between carboxylic acids and alcohols is approximately equal. In 2000, Yamamoto et al. reported that 0.1 to 1.0 mol% hafnium (IV) salts in toluene at reflux condition catalyzed the condensation reaction of equimolar amount of carboxylic acids and alcohols (Table 2, entry 1) [38, 39, 40, 41, 42, 43, 44, 45, 46, 47]. Since then, various types of catalysts have been found for the effective esterification reactions. Selected examples are summarized in Table 2. Diphenylammonium triflate (entry 2) [48], fluoroalkyldistannoxane (entry 3) [49], HClO4-SiO2 (entry 4) [50, 51, 52], Ti4+-mont (mont = montmorillonite, entry 5) [53], bulky diarylammonium arenesulfonates (entry 6) [54, 55, 56, 57, 58], Zn(ClO4)2-6H2O (entry 7) [59], pentafluorophenylammonium triflate (entry 8) [60], TsOH or CSA (entry 9) [61], phosohorofluoridic acid (entry 10) [62], N,N-diarylammonium pyrosulfates in H2O (entry 11) [63, 64], TfOH in Solkane365mfc (entry 12) [65], 2-oleamido-5-nitro-pyridinium p-toluenesulfonate (entry 13) [66], zirconocene complex (entry 14) [67], and L-leucine as an organocatalyst (entry 15) [68] have been reported for the effective catalyst for the esterification using equal or nearly equal amount of carboxylic acids and alcohols.

Table 2.

Representative progresses for the synthesis of esters using equal or nearly equal amount of carboxylic acids and alcohols in the presence of the catalyst, since 2000 (selected examples).

Another approach for the esterification of carboxylic acids with alcohols (2 equiv.) was developed by Kobayashi and coworkers [69, 70, 71], in which p-dodecylbenzenesulfonic acid (DBSA) was used as a surfactant-type catalyst in water (Scheme 2). Because the micelles of DBSA are produced, the esterification reactions between carboxylic acid and alcohol proceed in the micelles. After the reaction, the micelle releases H2O. The carboxylic acids and alcohols bearing the longer alkyl chains seem to be favored because of the increase of the hydrophobicity. Thus, the equilibrium between starting materials and the product lies in right side.

Scheme 2.

The use of DBSA in H2O solvent (Kobayashi [69, 70]). The reactions were conducted in the ratio of RCOOH (1 equiv.) and R’OH (2 equiv.).

The use of resin was also reported by Uozumi et al., who designed and synthesized the porous phenolsulfonic acid formaldehyde resin (PAFR) from 4-hydroxybenzenesulfonic acid and formaldehyde (5 equiv.) in H2O (Scheme 3). The solid resin was allowed to react with RCOOH and R’OH to give the corresponding esters in good yields [72, 73]. The merit of the resin is that it can be recovered by the simple filtration and reused without the significant loss of the catalytic activity. Other type of solid catalysts bearing SO3H unit are also reported. For examples, polystyrene-supported sulfonic acid catalyst [74], SBA-15-functionalized propylsulfonic acid catalyst [75], p-sulonic acid calix[n]arenes catalyst [76], β-cyclodextrin-derived carbonaceous catalyst [77], and sulfonated hyperbranched poly(aryleneoxindole) acid catalyst [78] are developed and utilized for the esterification.

Scheme 3.

The use of PAFR as the condensation catalyst (Uozumi [72, 73]).

As for the promising reaction tool for the esterification, the use of the flow chemistry has emerged. For example, Uozumi et al. applied the PAFR to the flow method [72, 73]. Fukuyama et al. demonstrated Fisher esterification by the flow system, in which silica bearing terminal -SO3H group was used [79, 80].

Advertisement

3. Synthesis of carboxylic acid esters using carboxylic acids as nucleophiles

3.1. Nucleophilic reactions of carboxylate ion intermediates

3.1.1. The use of bases and ionic liquids

Because the acidity of carboxylic acids is relatively high, it is easy to generate and accumulate the carboxylate ion intermediates by the deprotonation of carboxylic acids. SN2 reaction of carboxylate ions with alkyl halides is one of the most popular approaches, when carboxylate ions can be used as the nucleophiles. It was found that CsF or KF is the effective base toward carboxylic acids by Clark and Miller [81]. Since then, various reactions have been reported in these fields. Recent examples of this chemistry utilize the combination of bases (such as Huning’s base, Et3N and KF) and various ionic liquids (such as imidazolium salts and phosphonium salts), summarized in Figure 1 [82, 83, 84, 85, 86, 87, 88, 89, 90]. The countercations of carboxylate ions are bulky cations such as imidazolium salts and phosphonium salts, which seem to increase the reactivity of the carboxylate ions toward electrophiles.

Figure 1.

Recent and selected examples for nucleophilic reactions using carboxylate ion intermediates in various ionic liquids.

It has been well known so far that F− source such as KF and CsF can serve as good base toward carboxylic acids, described above [81]. Because of this reason, Bu4NF is also the attractive reagent for the deprotonation of carboxylic acid. In 2001, Maruoka et al. reported in situ generation of Bu4NF from the combination of a catalytic amount of Bu4NHSO4 (5 mol%) and KF-H2O (5 equiv.), which takes the proton of carboxylic acids to generate reactive carboxylate ion intermediates, whose countercation is presumably bulky Bu4N+ (Scheme 4(a)) [91]. In addition, Matsumoto et al. also reported the reactions of carboxylic acids with a stoichiometric amount of Bu4NF cleanly generated and accumulated reactive carboxylate ion intermediates, which reacted with various alkyl halides to give the corresponding esters in moderate to good yields (Scheme 4 (b)) [92].

Scheme 4.

Nucleophilic reactions of carboxylate ion intermediates by using Bu4NF as the base. (a) in situ generation of a catalytic amount of Bu4NF (Maruoka [91]). (b) the use of a stoichiometric amount of Bu4NF (Matsumoto [94]).

The use of good affinity of F− and metals such as Si and Sn was also developed in order to generate and accumulate highly reactive carboxylate ion intermediates. For example, the reaction of silyl-protected carboxylic acids with Ph3CF in the presence of a small amount of SiF4 produced the corresponding esters, in which SiF4 might activate both silyl-protected carboxylic acids (substrates) and Ph3C-F to generate carboxylate ions and Ph3C+, respectively (Scheme 5(a), Noyori et al.) [93]. The combination of silyl-protected carboxylic acids and Bu4NF was also reported by Maruoka et al. (Scheme 5 (b)) [94]. Nozaki et al. reported the use of Sn in 1992. The intermediate bearing COO-Sn bond reacted with alkyl halides in the presence of CsF, as shown in Scheme 5 (c) [95].

Scheme 5.

The use of affinity of F− and metals such as Si and Sn to generate carboxylate ion intermediates.

3.1.2. The use of electrochemical reduction methods

Electrochemistry is a clean technique, and basically the electron serves as the reagent instead of chemical reagents [96, 97, 98, 99]. Therefore, electrochemistry in organic synthesis does not generate the waste derived from reagents, and is recognized as one of the powerful tools for green chemistry. The pioneering work for the esterification of carboxylic acids and alkyl halides using electrochemistry was developed by Nonaka et al. (Scheme 6) [100, 101]. The solution containing carboxylic acids underwent electrochemical reduction to generate highly reactive carboxylate ions, which reacted with alkyl halides to produce the corresponding esters. Matsumoto et al. investigated the detailed reaction condition, the scope and limitations, and the mechanism of the electroreductive esterification reaction (Scheme 6) [102].

Scheme 6.

Electrochemical reduction condition to generate carboxylate ion intermediates followed by esterification. * The electro-reductive esterification of carboxylic acids in the presence of alkyl halides was also examined.

The use of electro-generated base (EGB) [97] is also effective to generate reactive carboxylate ion intermediates, developed by Shono et al. (Scheme 7) [103]. 2-Pyrrolidone was electrochemically reduced and 2-pyrrolidone anion was generated and accumulated as the base in the solution phase, which reacted with carboxylic acids to generate carboxylate ions bearing the quaternary ammonium cation. The reaction was applicable to the formation of macrolides.

Scheme 7.

Electrochemical preparation of EGB (electro-generated base) and its utilization for the esterification (Shono and Kashimura [103]).

3.1.3. The use of electrophile equivalents

Some substrates were found to be effective as the electrophile equivalents, when carboxylic acids served as the nucleophile (Figure 2). For example, One of the interesting examples is the use of 2-benzyloxy-1-methylpyridinium triflate reported by Dudley (Figure 2(a)) [104]. The benzyl cation was gradually generated, which was allowed to react with carboxylic acids. The in situ version was also established by Albiniak et al. [105]. Cu-mediated coupling reactions using aryl trialkoxysilanes [106] or arylboronic acids [107] were developed by Cheng et al. (Figure 2(b)). Diaryliodonium salts were found to be good electrophiles for the esterification (Figure 2(c)) [108]. Meier et al. reported the use of diphenyl carbonate as the electrophile to produce phenyl esters (Figure 2(d)) [109, 110]. Kunishima et al. found that 2,4,6-tris(benzyloxy)-1,3,5-triazine (TriBOT) serves as the benzyl cation equivalent via SN2 mechanism in the presence of a catalytic amount of TfOH at room temperature (Figure 2(e)) [111]. The reaction at high temperature also proceeded without TfOH. Thus, O-benzylation of carboxylic acids took place smoothly. This methodology was extended to the use of 2,4,6-tris(tert-butoxy)-1,3,5-triazine (TriAT-tBu), in which carboxylic acids can react with the tert-butyl cation via SN1 mechanism to afford the corresponding esters (Figure 2(e)) [112, 113]. The reactions of the diphenylmethyl trichloroacetimidate with carboxylic acids were also investigated by Chisholm et al. [114, 115].

Figure 2.

Selected examples for the use of electrophile equivalents.

Recently, dimethyl sulfoxide (DMSO) was utilized for the source of CH3- unit in the reaction with carboxylic acids to give the methyl esters shown in Scheme 8. The generation of methyl radical was indicated [116].

Scheme 8.

Methyl esterification of carboxylic acids using DMSO (Guo [116]).

In situ generation of benzyl bromide from toluene derivatives by using NaBrO3/NaHSO3, followed by the nucleophilic reactions of the carboxylic acids could be achieved by Khan et al. (Scheme 9) [117]. Although aliphatic carboxylic acids were not suitable, the aromatic carboxylic acids can be converted to the corresponding esters.

Scheme 9.

In situ formation of benzyl bromide as the electrophile equivalent (Khan [117]).

3.2. The use of the functionalization of C-–H bonds

Recently, the esterification of carboxylic acids and suitable substrates via the functionalization of C-H bond has been extensively studied. For example, Zhang et al. found that the reaction of carboxylic acids and toluene in the presence Pd(OAc)2 (10 mol%), CF3SO3H (10 mol%) and N,N-dimethylacetamide (1 equiv.) under O2 (1 atm) afforded the corresponding esters via benzylic C-H bond activation (Scheme 10) [118]. Other interesting examples of this approach have been extensively studied [119, 120, 121, 122, 123, 124, 125].

Scheme 10.

Esterification of carboxylic acids and toluene catalyzed by Pd(OAc)2 (Zhang [118]).

3.3. The use of metal catalysts

The addition of carboxylic acids onto C-C multiple bonds proceeds with high atom efficiency to afford the corresponding enol or alkyl esters. Hg salts have been used as the catalysts for these reactions for a long time; however, the use of these toxic salts should be avoided from the view point of green chemistry. Ruthenium complexes have been paid much attention for the alternative catalyst for the addition of carboxylic acids onto C-C multiple bonds. These ruthenium-catalyzed addition reactions of carboxylic acids to alkynes and several catalytic formation of alkyl esters by the addition of carboxylic acids to alkenes are summarized in this section.

3.3.1. The addition of carboxylic acids onto alkynes

The addition reaction of carboxylic acids onto alkynes with ruthenium catalysts through the Markovnikov’s rule was well investigated by Mitsudo and Dixneuf, independently [126, 127, 128]. In 1987, Mitsudo and coworkers reported that the reaction of carboxylic acids including N-protected α-amino acids with alkynes were performed in the presence of Ru(η5-cod)2, phosphine ligands and maleic anhydride in toluene to afford the corresponding enol esters in 31–99% yields (Scheme 11) [126]. This reaction proceeds with the high regioselectivity (>89% selectivity).

Scheme 11.

Markovnikov addition (Mitsudo [126]).

On the other hand, Dixneuf and coworkers developed the simpler catalytic system for the Markovnikov addition. Thus, (p-cymene)RuCl2(PPh3) catalyzed the addition of carboxylic acids to the alkynes to give the corresponding adducts in high yields (78–92%), as shown in Scheme 12 [127, 128]. They also found the highly selective anti-Markovnikov addition by the use of Ru(η3-methallyl)2(diphosphine) (diphosphine = dppb or dppe) to obtain the Z-enol esters in high yields with regio- and Z-selectivities (Scheme 13) [129, 130, 131, 132].

Scheme 12.

Markovnikov addition (Dixneuf [127, 128]).

Scheme 13.

Anti-Markovnikov addition of carboxylic acids onto terminal alkynes (Dixneuf [129, 130, 131, 132]).

The reaction mechanisms for both regioselective additions were proposed by Dixneuf et al. (Scheme 14), and the formation of vinylidene complex is crucial for the anti-Markovnikov addition. Thus, the Markovnikov adducts are formed through the activation of alkynes by the formation of π-complex with ruthenium catalyst, followed by the nucleophilic attack of the carboxylate ion onto the internal carbon atom of alkynes and the protonolysis of Ru-C δ-bond [128]. On the other hand, the anti-Markovnikov adducts are afforded by the vinylidene complex formation between the ruthenium catalyst and alkynes, followed by the nucleophilic attack of the carboxylate ion to the terminal carbon of alkynes and the protonolysis of the resulting intermediate [129].

Scheme 14.

Reaction mechanisms of the present enol ester formations.

Two simple catalytic systems, in which the regioselectivity is easily controlled by the use of the same or similar catalyst, have been reported [133, 134]. Goossen et al. found that the reaction of carboxylic acids and alkenes with RuCl2(p-cymene)/phosphine catalyst in the presence of K2CO3 gave the corresponding Markovnikov adducts in good to excellent yields, whereas the use of DMAP instead of K2CO3 afforded the anti-Markovnikov (Z) esters in high yields (Scheme 15) [133]. The reactions with RuClH(CO)(PCy)3 catalyst showed the interesting solvent-controlled regioselectivity (Scheme 16) [134]. Thus, the reaction of benzoic acid with aryl acetylene in the presence of RuClH(CO)(PCy)3 as a catalyst in CH2Cl2 gave the Markovnikov adducts in high yields. On the other hand, the use of THF as a solvent instead of CH2Cl2 led to the inverse of the selectivity to afford the corresponding anti-Markovnikov (Z) esters in high yields together with the high selectivity. It is considered that the use of THF accelerated the formation of vinylidene complex intermediates. Unfortunately, this interesting effect was not observed in the reaction of aliphatic alkynes.

Scheme 15.

Regioselective addition (Goossen [133]).

Scheme 16.

Solvent-controlled selective additions (Yi [134]).

The stereoselective formation of anti-Markovnikov (E) esters is so far limited [135, 136, 137]. Verpoort [135], Leong [136] and Fan [137] and their coworkers showed the (E)-selective formation of enol esters with their own ruthenium catalyst (Scheme 17), independently. However, the E/Z ratios were dependent on the alkyne and/or substrates of carboxylic acids. The rhenium catalyst showed the E-selectivity, though the selectivity was also strongly dependent on the substrates of alkynes. Similar selectivity was obtained when Re(CO)5Br was used as a catalyst, though the E/Z ratios were moderate (Scheme 18) [138].

Scheme 17.

Ruthenium catalysts for E-selective additions.

Scheme 18.

Rhenium catalysis for additions of carboxylic acids onto alkynes (Hua [138]).

Two examples for the regio- and E-selective addition of carboxylic acids onto “internal” alkynes have been reported (Scheme 19). Lang et al. found that the reaction of the carboxylic acid with symmetrical internal alkynes in the presence of [Ru(CO)2{(p-CF3C6H4)3P}(O2CPh)2]/B(C6F5)3 catalyst afforded the corresponding E-enol esters in up to 99% yield with the extremely high E-selectivity [139]. This catalytic system also achieved the regio- and stereoselective addition of carboxylic acids to unsymmetrical internal alkynes, in which the E/Z ratio reached up to 72:28. Kawatsura and Itoh reported the reaction with alkynes having trifluoromethyl and aryl group [140]. The reaction proceeded with high regioselectivity and stereoselectivity to provide the corresponding (E)-enol esters including trifluoromethyl group in up to 92% yield.

Scheme 19.

Regio- and stereoselective additions to unsymmetrical internal alkynes.

3.3.2. The addition of carboxylic acids onto alkenes

In 2004, Oe et al. reported the first transition metal-catalyzed addition of carboxylic acids onto alkenes. Thus, the reaction of benzoic acids with norbornene was carried out in the presence of [Cp*RuCl2]2/AgOTf/Dppb catalyst in toluene at 85 °C to obtain the corresponding norbornyl benzoates in good to high yields (Scheme 20) [141]. After that, several metal catalysts for the addition of carboxylic acids to alkenes have been reported and are summarized in Table 3.

Scheme 20.

Ruthenium-catalyzed additions of carboxylic acids to norbornene (Oe [141]).

Table 3.

Recent reported catalysts and generality of alkene substrates.

Norbornene is a generally good substrate due to the strain of the C–C double bond, therefore the reported catalyst afforded the corresponding esters in high yields (Table 3) [142, 143, 144, 145]. In 2005, He et al. reported the Au catalyst, where the four alkenes including unstrained 1-octene were transformed into the corresponding esters in 75–95% yields (entry 1) [142]. Hii et al. showed the catalytic activity of Cu(OTf)2, though only norbornene was used as an alkene substrate (entry 2) [143]. In these cases, the addition of phenols onto alkenes was also catalyzed under the similar reaction conditions. With only norbornene, In(OTf)3 was also found as a good catalyst under the solvent-free reaction condition (entry 3) [144]. An ubiquitous iron catalysis has been reported by Sakakura et al., where the unstable ester such as acrylates can be synthesized under the solvent-free reaction conditions (entry 4) [145]. Modified ruthenium(II) catalysis including xantphos ligand improved the scope of substrates of alkenes compared to that with ruthenium(III) catalyst to afford the corresponding esters in up to 99% yield by Oe et al. (entry 5) [146].

Hartwig and He found that TfOH itself showed the catalytic activity for the present addition reactions (Scheme 21) [147, 148]. Interestingly, the relatively large amount of catalyst and/or higher reaction temperature decreased the chemical yield of the product. It might be due to the polymerization of substrates of alkenes. Accompanied with the importance of triflate in the metal-catalyzed reaction described above, these metal catalysts might act as a TfOH source.

Scheme 21.

TfOH-catalyzed reactions.

Recently, an organocatalytic addition under the LED light irradiation conditions have been reported by Nicewicz et al. (Scheme 22) [149]. The reaction of carboxylic acids and internal and/or cyclic alkenes proceeds nicely under mild conditions to afford the corresponding esters in up to 99% yield regio-selectively.

Scheme 22.

The additions of carboxylic acids onto alkenes in the presence of the organocatalyst under the LED irradiation (Nicewicz [149]).

Advertisement

4. Conclusion

In this chapter, the recent progress of the esterification reactions using carboxylic acids as the starting material was overviewed, together with some basic and pioneering works. Various reagents, catalysts, synthetic media, and methods have been developed so far, and the quality of this field seems to be obviously increased. Because the topic of the efficient synthesis of esters is still an important task, it is expected that more innovative approach is discovered in near future.

References

  1. 1. Otera J, Nishikido J. Esterification: Methods, Reactions, and Applications, 2nd ed. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA; 2009. DOI: 10.1002/9783527627622
  2. 2. Siengalewicz P, Mulzer J, Rinner U. Synthesis of Esters and Lactones. In: Knochel P, Molander GA, editors. Comprehensive Organic Synthesis. 2nd ed; 2014;6:355-410. DOI: 10.1016/B978-0-08-097742-3.00612-1
  3. 3. Li JJ, Corey EJ, editors. Carboxylic Acid Derivatives Synthesis, in Name Reactions for Functional Group Transformations. Hoboken, NJ, USA: John Wiley & Sons, Inc; 2007. DOI: 10.1002/9780470176511.ch6
  4. 4. Neises B, Steglich W. Simple method for the esterification of carboxylic acids. Angewantde Chemie International Edition England. 1978;17:522-524. DOI: 10.1002/anie.197805221. DIC (N,N'-diisopropylcarbodiimide) is also recognized as a useful reagent for the alternation of DCC
  5. 5. Mitsunobu O, Yamada M. Preparation of esters of carboxylic and phosphoric acid via quaternary phosphonium salts. Bulletin Chemical Society of Japan. 1967;40:2380-2382. DOI: 10.1246/bcsj.40.2380
  6. 6. Hirose D, Gazvoda M, Kosmrlj J, Taniguchi T. Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents. Chemical Science. 2016;7:5148-5159. DOI: 10.1039/C6SC00308G. Recent reports of catalytic versions of Mitsunobu reaction
  7. 7. Hirose D, Taniguchi T, Ishibashi H. Recyclable Mitsunobu reagents: Catalytic Mitsunobu reactions with an iron catalyst and atmospheric oxygen. Angewandte Chemie, International Edition. 2013;52:4613-4617. DOI: 10.1002/anie.201300153. Recent reports of catalytic versions of Mitsunobu reaction
  8. 8. But TYS, Toy PH. Organocatalytic Mitsunobu reactions. Journal of the American Chemical Society. 2006;128:9636-9637. DOI: 10.1021/ja063141v. Recent reports of catalytic versions of Mitsunobu reaction
  9. 9. Mukaiyama T, Usui M, Shimada E, Saigo K. Convenient method for the synthesis of carboxylic esters. Chemistry Letters. 1975:1045-1048. DOI: 10.1246/cl.1975.1045
  10. 10. Funasaka S, Mukaiyama T. A versatile, practical, and inexpensive reagent, pyridine-3-carboxylic anhydride (3-PCA), for condensation reactions. Bulletin Chemical Society of Japan. 2008;81:148-159. DOI: 10.1246/bcsj.81.148, and references therein
  11. 11. Castro B, Dormoy J, Evin G, Selve C. Reactifs de couplage peptidique I (1) - l'hexafluorophosphate de benzotriazolyl N-oxytrisdimethylamino phosphonium (B.O.P.). Tetrahedron Letters. 1975;16:1219. DOI: 10.1016/S0040-4039(00)72100-9
  12. 12. Kim MH, Patel DV. BOP as a reagent for mild and efficient preparation of esters. Tetrahedron Letters. 1994;31:5603-5606. DOI: 10.1016/S0040-4039(00)77257-1
  13. 13. Paul R, Anderson GW. N,N'-Carbonyldiimidazole, a new peptide-forming reagent. Journal of the American Chemical Society. 1960;82:4596-4600. DOI: 10.1021/ja01502a038
  14. 14. For example of reviews, Armstrong A, Li W. N,N’-Carbonyldiimidazole. e-EROS Encyclopedia of Reagents for Organic Synthesis. 2007. DOI: 10.1002/9780470842898.rc024.pub2
  15. 15. Kunishima M, Kawachi C, Iwasaki F, Terao K, Tani S. Synthesis and characterization of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride. Tetrahedron Letters. 1999;40:5327-5330. DOI: 10.1016/S0040-4039(99)00968-5
  16. 16. Kunishima M, Morita J, Kawachi C, Iwasaki F, Terao K, Tani S. Esterification of carboxylic acids with alcohols by 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM). Synlett. 1999:1255-1256. DOI: 10.1055/s-1999-2828
  17. 17. Kunishima M, Kawachi C, Morita J, Terao K, Iwasaki F, Tani S. 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride: An efficient condensing agent leading to the formation of amides and esters. Tetrahedron. 1999;55:13159-13170. DOI: 10.1016/S0040-4020(99)00809-1
  18. 18. Valeur E, Bradley M. One of the excellent reviews for condensation regents including uronium based coupling reagents. Chemical Society Reviews. 2009;38:606-631. DOI: 10.1039/b701677h
  19. 19. The following catalog was referred for making this paragraph. Condensation reagents catalog for organic synthesis, 2nd ed, Wako Pure Chemical Industries (written in Japanese), and references therein
  20. 20. Pathak G, Das D, Rokhum L. A microwave-assisted highly practical chemoselective esterification and amidation of carboxylic acids. RSC Advances. 2016;6:93729-93740. DOI: 10.1039/C6RA22558F
  21. 21. Choi MKW, He HS, Toy PH. Direct radical polymerization of 4-styryldiphenylphosphine: Preparation of cross-linked and non-cross-linked Triphenylphosphine-containing polystyrene polymers. The Journal of Organic Chemistry. 2003;68:9831-9834. DOI: 10.1021/jo035226+. See also, the polymer-supported PPh3 mediated esterification
  22. 22. Jaita S, Phakhodee W, Pattarawarapan M. Ultrasound-assisted methyl esterification of carboxylic acids catalyzed by polymer-supported triphenylphosphine. Synlett. 2015;26:2006-2008. DOI: 10.1055/s-0034-1381117. See also, the polymer-supported PPh3 mediated esterification
  23. 23. Pathak G, Rokhum L. Selective monoesterification of symmetrical diols using resin-bound triphenylphosphine. ACS Combinatorial Science. 2015;17:483-487. DOI: 10.1021/acscombsci.5b00086. See also, the polymer-supported PPh3 mediated esterification
  24. 24. Mamidi N, Manna D. Zn(OTf)2-promoted chemoselective esterification of hydroxyl group bearing carboxylic acids. The Journal of Organic Chemistry. 2013;78:2386-2396. DOI: 10.1021/jo302502r
  25. 25. Garegg PJ, Samuelsson B. Novel reagent system for converting a hydroxy group into an iodo group in carbohydrates with inversion of configuration. Journal of the Chemical Society, Chemical Communications. 1979:978-980. DOI: 10.1039/c39790000978
  26. 26. Morcillo SP, de Cienfuegos LA, Mota AJ, Justicia J, Robles R. Mild method for the selective esterification of carboxylic acids based on the Garegg-Samuelsson reaction. The Journal of Organic Chemistry. 2011;76:2277-2281. DOI: 10.1021/jo102395c
  27. 27. Nowrouzi N, Mehranpour AM, Rad JA. A simple and convenient method for preparation of carboxylic acid alkyl esters, phenolic and thioesters using chlorodiphenylphosphine/I2 and imidazole reagent system. Tetrahedron. 2010;66:9596-9601. DOI: 10.1016/j.tet.2010.10.022
  28. 28. Salome C, Kohn H. Triphenylphosphine dibromide: A simple one-pot esterification reagent. Tetrahedron. 2009;65:456-460. DOI: 10.1016/j.tet.2008.10.062
  29. 29. Chen H, Xu X, Liu L, Tang G, Zhao Y. Phosphorus oxychloride as an efficient coupling reagent for the synthesis of esters, amides and peptides under mild conditions. RSC Advances. 2013;3:16247-16250. DOI: 10.1039/c3ra42887g
  30. 30. Dinesh M, Ranganathan R, Archana S, Sathishkumar M, Roshan B, Mohamed S, Ponnuswamy A. Staudinger's phosphazene as an efficient esterifying reagent. Synthetic Communication. 2016;46:1454-1460. DOI: 10.1080/00397911.2016.1211705
  31. 31. Tian J, Gao W, Zhou D, Zhang C. Recyclable hypervalent iodine(III) reagent iodosodilactone as an efficient coupling reagent for direct esterification, amidation, and peptide coupling. Organic Letters. 2012;14:3020-3023. DOI: 10.1021/ol301085v
  32. 32. Boulogeorgou MA, Triantakonstanti VV, Gallos Jn K. The system PhIO/Ph3P as an efficient reagent for mild and direct coupling of alcohols with carboxylic acids. ARKIVOC 2015:244-251. DOI: 10.3998/ark.5550190.p008.997
  33. 33. Rodrigues RC, Barros IMA, Lima ELS. Mild one-pot conversion of carboxylic acids to amides or esters with Ph3P/trichloroisocyanuric acid. Tetrahedron Letters. 2005;46:5945-5947. DOI: 10.1016/j.tetlet.2005.06.127
  34. 34. Taniguchi T, Hirose D, Ishibashi H. Esterification via iron-catalyzed activation of triphenylphosphine with air. ACS Catalysis. 2011;1:1469-1474. DOI: 10.1021/cs2003824
  35. 35. Marz M, Chudoba J, Kohout M, Cibulka R. Photocatalytic esterification under Mitsunobu reaction conditions mediated by flavin and visible light. Organic & Biomolecular Chemistry. 2017;15:1970-1975. DOI: 10.1039/C6OB02770A
  36. 36. Vandamme M, Bouchard L, Gilbert A, Keita M, Paquin J. Direct esterification of carboxylic acids with perfluorinated alcohols mediated by XtalFluor-E. Organic Letters. 2016;18:6468-6471. DOI: 10.1021/acs.orglett.6b03365
  37. 37. Nguyen TV, Lyons DJM. A novel aromatic carbocation-based coupling reagent for esterification and amidation reactions. Chemical Communications. 2015;51:3131-3134. DOI: 10.1039/C4CC09539A
  38. 38. Ishihara K, Ohara S, Yamamoto H. Direct condensation of carboxylic acids with alcohols catalyzed by hafnium(IV) salts. Science. 2000;290:1140-1142. DOI: 10.1126/science.290.5494.1140
  39. 39. Ishihara K, Nakayama M, Ohara S, Yamamoto H. A green method for the selective esterification of primary alcohols in the presence of secondary alcohols or aromatic alcohols. Synlett. 2001, 1117-1120. DOI: 10.1055/s-2001-15156
  40. 40. Ishihara K, Nakayama M, Ohara S, Yamamoto H. Direct ester condensation from a 1:1 mixture of carboxylic acids and alcohols catalyzed by hafnium(IV) or zirconium(IV) salts. Tetrahedron. 2002;58:8179-8188. DOI: 10.1016/S0040-4020(02)00966-3
  41. 41. Nakayama M, Sato A, Ishihara K, Yamamoto H. Water-tolerant and reusable catalysts for direct ester condensation between equimolar amounts of carboxylic acids and alcohols. Advanced Synthesis and Catalysis. 2004;346:1275-1279. DOI: 10.1002/adsc.200404149
  42. 42. Mantri, K, Nakamura R, Komura K, Sugi Y. Esterification of long chain aliphatic acids with long chain alcohols catalyzed by multi-valent metal salts. Chemistry Letters. 2015;34:1502-1503. DOI 10.1246/cl.2005.1502
  43. 43. Mantri K, Komura K, Sugi Y. ZrOCl2-8H2O catalysts for the esterification of long chain aliphatic carboxylic acids and alcohols. The enhancement of catalytic performance by supporting on ordered mesoporous silica. Green Chemistry. 2005;7:677-682. DOI: 10.1039/b504369g
  44. 44. Chen C, Munot YS. Direct atom-efficient esterification between carboxylic acids and alcohols catalyzed by amphoteric, water-tolerant TiO(acac)2. The Journal of Organic Chemistry 2005;70:8625-8627. DOI: 10.1021/jo051337s
  45. 45. Sato A, Nakamura Y, Maki T, Ishihara K, Yamamoto H. Zr(IV)-Fe(III), −Ga(III), and -Sn(IV) binary metal complexes as synergistic and reusable esterification catalysts. Advanced Synthesis and Catalysis. 2005;347:1337-1340. DOI: 10.1002/adsc.200505083
  46. 46. Mantri K, Komura K, Sugi Y. Efficient esterification of long chain aliphatic carboxylic acids with alcohols over ZrOCl2·8H2O catalyst. Synthesis. 2005:1939-1944. DOI: 10.1055/s-2005-869951
  47. 47. Nakamura Y, Maki T, Wang X, Ishihara K, Yamamoto H. Iron(III)-zirconium(IV) combined salt immobilized on N-(polystyrylbutyl) pyridinium triflylimide as a reusable catalyst for a dehydrative esterification reaction. Advanced Synthesis and Catalysis. 2006;348:1505-1510. DOI: 10.1002/adsc.200606126
  48. 48. Wakasugi K, Misaki T, Yamada K, Tanabe Y. Diphenylammonium triflate (DPAT): Efficient catalyst for esterification of carboxylic acids and for transesterification of carboxylic esters with nearly equimolar amounts of alcohols. Tetrahedron Letters. 2000;41:5249-5252. DOI: 10.1016/S0040-4039(00)00821-2
  49. 49. Xiang J, Orita A, Otera J. Fluorous biphasic esterification directed towards ultimate atom efficiency. Angewandte Chemie, International Edition. 2002;41:4117-4119. DOI: 10.1002/1521-3773(20021104)41:21<4117::AID-ANIE4117>3.0.CO;2-4
  50. 50. Chakraborti AK, Gulhane R. Perchloric acid adsorbed on silica gel as a new, highly efficient, and versatile catalyst for acetylation of phenols, thiols, alcohols, and amines. Chemicall Communication. 2003;1896-1897. DOI: 10.1039/B304178F
  51. 51. Chakraborti AK, Singh B, Chankeshwara SV, Patel AR. Protic acid immobilized on solid support as an extremely efficient recyclable catalyst system for a direct and atom economical esterification of carboxylic acids with alcohols. Journalnal of Organic Chemistry. 2009;74:5967-5974. DOI: 10.1021/jo900614s
  52. 52. Chakraborti AK, Chankeshwara SV, Singh B. Indian patent. 2764/DEL/2007 (Dec 28, 2007)
  53. 53. Kawabata T, Mizugaki T, Ebitani K, Kaneda K. Highly efficient esterification of carboxylic acids with alcohols by montmorillonite-enwrapped titanium as a heterogeneous acid catalyst. Tetrahedron Letters. 2003;44:9205-9208. DOI: 10.1016/j.tetlet.2003.10.024
  54. 54. Ishihara K, Nakagawa S, Sakakura A. Bulky diarylammonium arenesulfonates as selective esterification catalysts. Journal of American Chemical Society. 2005;127:4168-4169. DOI: 10.1021/ja050223v
  55. 55. Sakakura A, Nakagawa S, Ishihara K. Bulky diarylammonium arenesulfonates as mild and extremely active dehydrative ester condensation catalysts. Tetrahedron. 2006;62:422-433. DOI: 10.1016/j.tet.2005.09.059. See also
  56. 56. Sakakura A, Watanabe H, Nakagawa S, Ishihara K. Unusual rate acceleration in Brønsted acid catalyzed dehydration reactions: Local hydrophobic environment in aggregated N-(2,6-diphenylphenyl)-N-mesitylammonium pentafluorobenzenesulfonates. Chemistry, an Asian Journal. 2007;2:477-483. DOI: 10.1002/asia.200600380
  57. 57. Sakakura A, Nakagawa S, Ishihara K. Direct ester condensation catalyzed by bulky diarylammonium pentafluorobenzenesulfonates. Nature Protocools. 2007;2:1746-1751. DOI: 10.1038/nprot.2007.254
  58. 58. Ishihara K. Dehydrative condensation catalyses. Tetrahedron. 2009;65:1085-1109. DOI: 10.1016/j.tet.2008.11.004. Review of esterification
  59. 59. Bartoli G, Boeglin J, Bosco M, Locatelli M, Massaccesi M, Melchiorre P, Sambri L. Highly efficient solvent-free condensation of carboxylic acids with alcohols catalyzed by zinc perchlorate hexahydrate, Zn(ClO4)2-6H2O. Advanced Synthesis and Catalysis. 2005;347:33-38. DOI: 10.1002/adsc.200404171
  60. 60. Funatomi T, Wakasugi K, Misaki T, Tanabe Y. Pentafluorophenylammonium triflate (PFPAT): An efficient, practical, and cost-effective catalyst for esterification, thioesterification, transesterification, and macrolactone formation. Green Chemistry. 2006;8:1022-1027. DOI: 10.1039/b609181b
  61. 61. Sakakura A, Koshikari Y, Ishihara K. Open-air and solvent-free ester condensation catalyzed by sulfonic acids. Tetrahedron Letters. 2008;49:5017-5020. DOI: 10.1016/j.tetlet.2008.06.058
  62. 62. Murai T, Tanaka N, Higashijima S, Miura H. Phosphorofluoridic acid-catalyzed condensation reaction of carboxylic acids with 1-arylalkyl alcohols leading to esters under solvent-free conditions. Chemistry Letters. 2009;38:668-669. DOI: 10.1246/cl.2009.668
  63. 63. Sakakura A, Koshikari Y, Akakura M, Ishihara K. Hydrophobic N,N-diarylammonium pyrosulfates as dehydrative condensation catalysts under aqueous conditions. Organic Letters. 2012;14:30-33. DOI: 10.1021/ol2027366
  64. 64. Igarashi T, Yagyu D, Naitoa T, Okumura Y, Nakajo T, Mori Y, Kobayashi S. Dehydrative esterification of carboxylic acids with alcohols catalyzed by diarylammonium p-dodecylbenzenesulfonates in water. Applied Catalysis B-Environment. 2012;119-120:304-307. DOI: 10.1016/j.apcatb.2012.03.001
  65. 65. Xu X, Azuma A, Taniguchi M, Tokunaga E, Shibata N. Efficient direct ester condensation between equimolar amounts of carboxylic acids and alcohols catalyzed by trifluoromethanesulfonic acid (TfOH) in Solkane365mfc. RSC Advances. 2013;3:3848-3852. DOI: 10.1039/c3ra00132f
  66. 66. Wang W, Liu H, Xu S, Gao Y. Esterification catalysis by pyridinium p-toluenesulfonate revisited-modification with a lipid chain for improved activities and selectivities. Synthetic Communication. 2013;43:2906-2912. DOI: 10.1080/00397911.2012.749990
  67. 67. Tang Z, Jiang Q, Peng L, Xu X, Li J, Qiu R, Au C. Zirconocene-catalyzed direct (trans)esterification of acyl acids (esters) and alcohols in a strict 1 : 1 ratio under solvent-free conditions. Green Chemistry. 2017;19:5396-5402. DOI: 10.1039/C7GC02174G
  68. 68. Kumar M, Thakur K, Sharma S, Nayal OS, Kumar N, Singh B, Sharma U. Solvent-free, L-leucine-catalyzed direct dehydrative esterification of carboxylic acids with alcohols: Direct synthesis of 3-alkoxy 1(3 H)-isobenzofuranone. Asian Journal of Organic Chemistry. 2018;7:227-231. DOI: 10.1002/ajoc.201700523
  69. 69. Manabe K, Sun X, Kobayashi S. Dehydration reactions in water. Surfactant-type Brønsted acid-catalyzed direct esterification of carboxylic acids with alcohols in an emulsion system. Journal of the American Chemical Society. 2001;123:10101-10102. DOI: 10.1021/ja016338q
  70. 70. Manabe K, Iimura S, Sun X, Kobayashi S. Dehydration reactions in water. Brønsted acid-surfactant-combined catalyst for ester, ether, thioether, and dithioacetal formation in water. Journal of American Chemical Society. 2002;124:11971-11978. DOI: 10.1021/ja026241j
  71. 71. Jing L, Li X J, Han Y C, Chu Y. The esterification in cyclohexane/DBSA/water microemulsion system. Colloids and Surface A. Physicochemical and Engineering Aspects. 2008;326:37-41. DOI: 10.1016/j.colsurfa.2008.05.008
  72. 72. Baek H, Minakawa M, Yamada YMA, Han JW, Uozumi Y. In-water and neat batch and continuous-flow direct esterification and transesterification by a porous polymeric acid catalyst. Scientific Reports. 2016;6:25925. DOI: 10.1038/srep25925
  73. 73. Minakawa M, Baek H, Yamada YMA, Han JW, Uozumi Y. Direct dehydrative esterification of alcohols and carboxylic acids with a macroporous polymeric acid catalyst. Organic Letters. 2013;15:5798-5801. DOI: 10.1021/ol4028495
  74. 74. Manabe K, Kobayashi S. Dehydrative esterification of carboxylic acids with alcohols catalyzed by polymer-supported sulfonic acids in water. Advanced Synthesis and Catalysis. 2002;344:270-273. DOI: 10.1002/1615-4169(200206)344:3/4<270::AID-ADSC270>3.0.CO;2-7
  75. 75. Karimi B, Vafaeezadeh M. SBA-15-functionalized sulfonic acid confined acidic ionic liquid: A powerful and water-tolerant catalyst for solvent-free esterifications. Chemical Communications. 2012;48:3327-3329. DOI: 10.1039/c2cc17702a
  76. 76. Fernandes SA, Natalino R, Gazolla PAR, da Silva MJ, Jham GN. p-sulfonic acid calix[n]arenes as homogeneous and recyclable organocatalysts for esterification reactions. Tetrahedron Letters. 2012;53:1630-1633. DOI: 10.1016/j.tetlet.2012.01.078
  77. 77. Thombal RS, Jadhav AR, Jadhav VH. Biomass derived β-cyclodextrin-SO3H as a solid acid catalyst for esterification of carboxylic acids with alcohols. RSC Advances. 2015;5:12981-12986. DOI: 10.1039/C4RA16699J
  78. 78. Verheyen T, Smet M, De Borggraeve WM. Water tolerant and reusable sulfonated hyperbranched poly(aryleneoxindole) acid catalyst for solvent-free esterification. Chemistry Select. 2017;2:9822-9828. DOI: 10.1002/slct.201701636
  79. 79. Furuta A, Fukuyama T, Ryu I. Efficient flow Fischer esterification of carboxylic acids with alcohols using sulfonic acid-functionalized silica as supported catalyst. Bulletin Chemical Society of Japan. 2017;90:607-612. DOI: 10.1246/bcsj.20170025
  80. 80. Audubert C, Lebel H. Mild esterification of carboxylic acids via continuous flow diazotization of amines. Organic Letters. 2017;19:4407-4410. DOI: 10.1021/acs.orglett.7b02231. See also another example using micro reactor. This reaction is categorized into 3.1 Nucleophilic reaction of carboxylate ion intermediate
  81. 81. Clark JH, Miller JM. Hydrogen bonding in organic synthesis. V. Potassium fluoride in carboxylic acids as an alternative to crown ether with acid salts in the preparation of phenacyl esters. Tetrahedron Letters. 1977;18:599. DOI: 10.1016/S0040-4039(01)92703-0. See also, the introduction of ref. 56
  82. 82. Cardellini F, Brinchi L, Germani R, Tiecco M. Convenient esterification of carboxylic acids by SN2 reaction promoted by a Protic ionic-​liquid system formed in situ in solvent-​free conditions. Synthetic Communications. 2014;44:3248-3256. DOI: 10.1080/00397911.2014.933353
  83. 83. Gok Y, Alici B, Cetinkaya E, Ozdemir I, Ozeroglu O. Ionic liquids as solvent for efficient esterification of carboxylic acids with alkyl halides. Turkish Journal of Chemistry. 2010;34:187-191. DOI: 10.3906/kim-0904-39
  84. 84. Judeh ZMA, Shen H, Chi BC, Feng L, Selvasothi S. A facile and efficient nucleophilic displacement reaction at room temperature in ionic liquids. Tetrahedron Letters. 2002;43:9381-9384. DOI: 10.1016/S0040-4039(02)02327-4
  85. 85. McNulty J, Cheekoori S, Nair J, Larichev V, Capretta A, Robertson A. A mild esterification process in phosphonium salt ionic liquid. Tetrahedron Letters. 2005;46:3641-3644. DOI: 10.1016/j.tetlet.2005.03.169
  86. 86. Brinchi L, Germani R, Savelli G. Ionic liquids as reaction media for esterification of carboxylate sodium salts with alkyl halides. Tetrahedron Letters. 2003;44:2027-2029. DOI: 10.1016/S0040-4039(03)00179-5
  87. 87. Brinchi L, Germani R, Savelli G. Efficient esterification of carboxylic acids with alkyl halides catalyzed by fluoride ions in ionic liquids. Tetrahedron Letters. 2003;44:6583-6585. DOI: 10.1016/S0040-4039(03)01693-9
  88. 88. Dighe S, Bhattad R, Kulkarni R, Jain K, Srinivasan K. A rapid and facile esterification of Na-carboxylates with alkyl halides promoted by the synergy of the combined use of DMSO and an ionic liquid under ambient conditions. Synthetic Communications. 2010;40:3522-3527. DOI: 10.1080/00397910903457357
  89. 89. Muskawar PN, Thenmozhi K, Gajbhiye M, Bhagat PR. Facile esterification of carboxylic acid using amide functionalized benzimidazolium dicationic ionic liquids. Applied Catalysis A. 2014;482:214-220. DOI: 10.1016/j.apcata.2014.06.004
  90. 90. Jadhav A H, Lee K, Koo S, Seo J G. Esterification of carboxylic acids with alkyl halides using imidazolium based dicationic ionic liquids containing bis-trifluoromethane sulfonimide anions at room temperature. RSC Advances. 2015;5:26197-26208. DOI: 10.1039/C5RA00802F
  91. 91. Ooi T, Sugimoto H, Doda K, Maruoka K. Esterification of carboxylic acids catalyzed by in situ generated tetraalkylammonium fluorides. Tetrahedron Letters. 2001;42:9245-9248. DOI: 10.1016/S0040-4039(01)02035-4
  92. 92. Matsumoto K, Shimazaki H, Miyamoto Y, Shimada K, Haga F, Yamada Y, Miyazawa H, Nishiwaki K, Kashimura S. Simple and convenient synthesis of esters from carboxylic acids and alkyl halides using tetrabutylammonium fluoride. Journal of Oleo Science. 2014;63:539-544. DOI: 10.5650/jos.ess13199
  93. 93. Hashimoto S, Hayashi M, Noyori R. An easy preparation of triphenylmethyl carboxylates. Bulletin of the Chemical Society of Japan. 1984;57:1431-1432. DOI: 10.1246/bcsj.57.1431
  94. 94. Ooi T, Sugimoto H, Maruoka K. Facile conversion of trialkylsilyl esters to alkyl esters mediated by tetrabutylammonium fluoride trihydrate. Heterocycles. 2001;54:593-596
  95. 95. Sato T, Otera J, Nozaki H. Cesium fluoride-promoted esterification of carboxylic acids. A practical alternative to the diazomethane method and direct conversion of organotin carboxylates. The Journal of Organic Chemistry. 1992;57:2166-2169. DOI: 10.1021/jo00033a048
  96. 96. Selected reviews of electro-organic chemistry, Yoshida J, Kataoka K, Horcajada R, Nagaki A. Modern strategies in electroorganic synthesis. Chemical Reviews. 2008;108:2265-2299. DOI: 10.1021/cr0680843. chemrev.7b00475, and references therein
  97. 97. Selected reviews of electro-organic chemistry, Frontana-Uribe BA, Little RD, Ibanez JG, Palma A, Vasquez-Medrano R. Organic electrosynthesis: A promising green methodology in organic chemistry. Green Chemistry. 2010;12:2099-2119. DOI: 10.1039/c0gc00382d. chemrev.7b00475, and references therein
  98. 98. Selected reviews of electro-organic chemistry, Sperry JB, Wright DL. The application of cathodic reductions and anodic oxidations in the synthesis of complex molecules. Chemical Society Reviews. 2006;35:605-621. DOI: 10.1039/b512308a. chemrev.7b00475, and references therein
  99. 99. Selected reviews of electro-organic chemistry, Yoshida J, Shimizu A, Hayashi R. Electrogenerated cationic reactive intermediates: The pool method and further advances. Chemical Review. in press. DOI: 10.1021/acs.chemrev.7b00475, and references therein
  100. 100. Awata T, Baizer M, Nonaka T, Fuchigami T. Cathodic esterification of carboxylic acids. Chemical Letters. 1985;3:371-374. DOI: 10.1246/cl.1985.371
  101. 101. Fuchigami T, Awata T, Nonaka T, Baizer MM. Esterification, etherification, and aldol condensation using cathodically generated organic olate anions. Bulletin Chemical Society Japan. 1986;59:2873-2879. DOI: 10.1246/bcsj.59.2873
  102. 102. Miyamoto Y, Yamada Y, Shimazaki H, Shimada K, Nokami T, Nishiwaki K, Kashimura S, Matsumotoa K. Esterification of carboxylic acids with alkyl halides using electroreduction Electrochemistry 2015;83:161-164. DOI: 10.5796/electrochemistry.83.161
  103. 103. Shono T, Ishige O, Uyama H, Kashimura S. Electroorganic chemistry. 91. A novel base useful for synthesis of esters and macrolides. The Journal of Organic Chemistry 1986;51:546-549. DOI: 10.1021/jo00354a030
  104. 104. Tummatorn J, Albiniak PA, Dudley GB. Synthesis of benzyl esters using 2-benzyloxy-1-methylpyridinium triflate. The Journal of Organic Chemistry. 2007;72:8962-8964. DOI: 10.1021/jo7018625
  105. 105. Strayer TA, Culy CC, Bunner MH, Frank AR, Albiniak PA. In situ synthesis of 2-allyloxy-1-methylpyridinium triflate for the allylation of carboxylic acids. Tetrahedron Letters. 2015;56:6807-6809. DOI: 10.1016/j.tetlet.2015.10.085
  106. 106. Luo F, Pan C, Qian P, Cheng J. Copper(II)-catalyzed esterification of arenecarboxylic acids with aryl- and vinyl-substituted trimethoxysilanes. Synthesis. 2010:2005-2010. DOI: 10.1055/s-0029-1218759
  107. 107. Zhang L, Zhang G, Zhang M, Cheng J. Cu(OTf)2-mediated Chan-lam reaction of carboxylic acids to access phenolic esters. The Journal of Organic Chemistry 2010;75:7472-7474. DOI: 10.1021/jo101558s
  108. 108. Petersen TB, Khan R, Olofsson B. Metal-free synthesis of aryl esters from carboxylic acids and diaryliodonium salts. Organic Letters. 2011;13:3462-3465. DOI: 10.1021/ol2012082
  109. 109. Kreye O, Meier MAR. Base catalyzed sustainable synthesis of phenyl esters from carboxylic acids using diphenyl carbonate. RSC advances. 2015;5:53155-53160. DOI: 10.1039/C5RA10206E
  110. 110. Shieh W, Dell S, Repic O. Tetrahedron Letters 2002;43:5607-5609. DOI: 10.1016/S0040-4039(02)01116-4
  111. 111. Yamada K, Yoshida S, Fujita H, Kitamura M, Kunishima M. O-benzylation of carboxylic acids using 2,4,6-Tris(benzyloxy)-1,3,5-triazine (TriBOT) under acidic or thermal conditions. European Journal of Organic Chemistry. 2015:7997-8002. DOI: 10.1002/ejoc.201501172
  112. 112. Kunishima M, Fujita H, Yamada K. PCT Int. Appl. WO 2013 073681 A1, 2013
  113. 113. Yamada K, Hayakawa N, Fujita H, Kitamura M, Kunishima M. Development of a triazine-based tert-Butylating reagent, TriAT-tBu. European Journal of Organic Chemistry. 2016:4093-4098. DOI: 10.1002/ejoc.201600663
  114. 114. Adhikari AA, Shah JP, Howard KT, Russo CM, Wallach DR, Linaburg MR, Chisholm JD. Convenient formation of diphenylmethyl esters using diphenylmethyl trichloroacetimidate. Synlett. 2014;25:283-287. DOI: 10.1055/s-0033-1340293
  115. 115. Shah JP, Russo CM, Howard KT, Chisholm JD. Spontaneous formation of PMB esters using 4-methoxybenzyl-2,2,2-trichloroacetimidate. Tetrahedron Letters. 2014;55:1740-1742. DOI: 10.1016/j.tetlet.2014.01.097
  116. 116. Jia J, Jiang Q, Zhao A, Xu B, Liu Q, Luo W, Guo C. Copper-catalyzed O-methylation of carboxylic acids using DMSO as a methyl source. Synthesis. 2016;48:421-428. DOI: 10.1055/s-0035-1560967
  117. 117. Khan KM, Maharvi GM, Hayat S, Zia-Ullah CMI, Rahman A-U. An expedient esterification of aromatic carboxylic acids using sodium bromate and sodium hydrogen sulfite. Tetrahedron. 2003;59:5549-5554. DOI: 10.1016/S0040-4020(03)00812-3
  118. 118. Liu H, Shi G, Pan S, Jiang Y, Zhang Y. Palladium-catalyzed benzylation of carboxylic acids with toluene via benzylic C-H activation. Organic Letters. 2013;15:4098-4101. DOI: 10.1021/ol401687f
  119. 119. Selected recent examples of this chemistry. Lu B, Zhu F, Sun H, Shen Q. Esterification of the primary benzylic C-H bonds with carboxylic acids catalyzed by ionic iron(III) complexes containing an imidazolinium cation. Organic Letters. 2017;19:1132-1135. DOI: 10.1021/acs.orglett.7b00148/C7RA02788E, and references therein
  120. 120. Selected recent examples of this chemistry. Zheng Y, Mao J, Rong G, Xu X. A NCS mediated oxidative C-H bond functionalization: Direct esterification between a C(sp3)-H bond and carboxylic acids. Chemical Communications. 2015;51;8837-8840. DOI: 10.1039/C5CC02424B/C7RA02788E, and references therein
  121. 121. Selected recent examples of this chemistry. Ren T, Xu B, Mahmood S, Sun M, Zhang S. Cobalt-catalyzed oxidative esterification of allylic/benzylic C(sp3)-H bonds. Tetrahedron. 2017;73:2943-2948. DOI: 10.1016/j.tet.2017.04.002/C7RA02788E, and references therein
  122. 122. Selected recent examples of this chemistry. Lu B, Zhu F, Wang D, Sun H, Shen Q. Iron-catalyzed esterification of allylic sp3 C-H bonds with carboxylic acids: Facile access to allylic esters. Tetrahedron Letters. 2017;58:2490-2494. DOI: 10.1016/j.tetlet.2017.05.039/C7RA02788E, and references therein
  123. 123. Selected recent examples of this chemistry. Dick AR, Hull KL, Sanford MS. A highly selective catalytic method for the oxidative functionalization of C-H bonds. Journal of the American Chemical Society. 2004;126:2300-2301. DOI: 10.1021/ja031543m/C7RA02788E, and references therein
  124. 124. Selected recent examples of this chemistry. Chen X, Hao X, Goodhue C E, Yu J. Cu(II)-catalyzed functionalizations of aryl C-H bonds using O2 as an oxidant. Journal of the American Chemical Society. 2006;128:6790-6791. DOI: 10.1021/ja061715q/C7RA02788E, and references therein
  125. 125. Selected recent examples of this chemistry. Mou F, Sun Y, Jin W, Zhang Y, Wang B, Liu Z, Guo L, Huang J, Liu C. Reusable ionic liquid-catalyzed oxidative esterification of carboxylic acids with benzylic hydrocarbons via benzylic Csp3-H bond activation under metal-free conditions. RSC Advances. 2017;7:23041-23045. DOI: 10.1039/C7RA02788E, and references therein
  126. 126. Mitsudo T, Hori Y, Yamakawa Y, Watanabe Y. Ruthenium-catalyzed selective addition of carboxylic acids to alkynes. A novel synthesis of enol esters. The Journal of Organic Chemistry. 1987;52:2230-2239. DOI: 10.1021/jo00387a024
  127. 127. Ruppin C, Dixneuf HP. Synthesis of enol esters from terminal alkynes catalyzed by ruthenium complexes. Tetrahedron Letters. 1986;52:6323-6324. DOI: 10.1016/S0040-4039(00)87798-9
  128. 128. Bruneau C, Neveux M, Kabouche Z, Ruppin C, Dixneuf HP. Ruthenium-catalysed additions to alkynes: Synthesis of activated esters and their use in acylation reactions. Synlett. 1991:755-763. DOI: 10.1055/s-1991-20866
  129. 129. Bruneau C, Dixneuf HP. Metal vinylidenes and allenylidenes in catalysis: Applications in Anti-Markovnikov additions to terminal alkynes and alkene metathesis. Angewantde Chemie International Edition. 2006;45:2176-2203. DOI: 10.1002/anie.200501391, and references therein
  130. 130. Dixneuf HP, Brueau C, Dérien S. Smart ruthenium catalysts for the selective catalytic transformation of alkynes. Pure and Applied Chemistry. 1998;70:1065-1070. DOI: 10.1351/pac199870051065
  131. 131. Doucet H, Martin-Veca B, Bruneau C, Dixneuf HP. General synthesis of (Z)-Alk-1-en-1-yl esters via ruthenium-catalyzed anti-Markovnikov trans-addition of carboxylic acids to terminal alkynes. The Journal of Organic Chemistry. 1995;60:7247-7255. DOI: 10.1021/jo00127a033
  132. 132. Doucet H, Höfer J, Bruneau C, Dixneuf HP. Stereoselective synthesis of Z-enol esters catalysed by [bis(diphenylphosphino)alkane]bis(2-methylpropenyl)ruthenium complexes. Journal of the Chemical Society, Chemical Communications. 1993:850-851. DOI: 10.1039/C39930000850
  133. 133. Goossen JL, Paetzolda J, Koleya D. Regiocontrolled Ru-catalyzed addition of carboxylic acids to alkynes: Practical protocols for the synthesis of vinyl esters. Chemical Communication. 2003:706-707. DOI: 10.1039/B211277A
  134. 134. Yi SC, Gao R. Scope and mechanistic investigations on the solvent-controlled regio- and stereoselective formation of enol esters from the ruthenium-catalyzed coupling reaction of terminal alkynes and carboxylic acids. Organometallics 2009;28:6585-6592. DOI: 10.1021/om9007357
  135. 135. Melis K, Samulkiewicz P, Rynkowski J, Verpoort F. Ruthenium-catalyzed selective anti-Markovnikov trans addition of carboxylic acids and tail-to-tail dimerization of terminal alkynes. Tetrahedron Letters. 2002;43:2713-2716. DOI: 10.1016/S0040-4039(02)00366-0
  136. 136. Ye S, Leong KW. Regio- and stereoselective addition of carboxylic acids to phenylacetylene catalyzed by cyclopentadienyl ruthenium complexes. Journal of Organometallic Chemistry. 2006;691:1117-1120. DOI: 10.1016/j.jorganchem.2005.11.023
  137. 137. Tan TS, Fan YW. Ligand-controlled regio- and stereoselective addition of carboxylic acids onto terminal alkynes catalyzed by carbonylruthenium(0) complexes. European Journal of Organic Chemistry. 2010:4631-4635. DOI: 10.1002/ejic.201000579
  138. 138. Hua R, Tian X. Re(CO)5Br-catalyzed addition of carboxylic acids to terminal alkynes: A high anti-Markovnikov and recoverable homogeneous catalyst. The Journal of Organic Chemistry. 2004;69:5782-5784. DOI: 10.1021/jo049455n
  139. 139. Jeschke J, Engelhardt BT, Lang H. Ruthenium-catalyzed hydrocarboxylation of internal alkynes. European Journal of Organic Chemistry. 2016:1548-1554. DOI: 10.1002/ejoc.201501583
  140. 140. Kawatsura M, Namioka J, Kajita K, Yamamoto M, Tsuji H, Itoh T. Ruthenium-catalyzed regio- and stereoselective addition of carboxylic acids to aryl and trifluoromethyl group substituted unsymmetrical internal alkynes. Organic Letters. 2011;13:3285-3287. DOI: 10.1021/ol201238
  141. 141. Oe Y, Ohta T, Ito Y. Ruthenium catalyzed addition reaction of carboxylic acid across olefins without β-hydride elimination. Chemical Communications. 2004:1620-1621. DOI: 10.1039/B404229H
  142. 142. Yang C, He C, Gold(I)-catalyzed intermolecular addition of phenols and carboxylic acids to olefins. Journal of the American Chemical Society. 2005;127:6966-6967. DOI: 10.1021/ja050392f
  143. 143. Taylor GJ, Whittall N, Hii KK. Copper(II)-catalysed addition of O–H bonds to norbornene. Chemical Communications. 2005:5103-5105. DOI: 10.1039/B509933A
  144. 144. Chen W, Lu J. In(OTf)3-catalyzed intermolecular addition of carboxylic acids and phenols to norbornene under solvent-free conditions. Catalysis Communications. 2007;8:1298-1300. DOI: 10.1016/j.catcom.2006.11.031
  145. 145. Choi J, Kohno K, Masuda D, Yasuda H, Sakakura T. Iron-catalysed green synthesis of carboxylic esters by the intermolecular addition of carboxylic acids to alkenes. Chemical Communications. 2008:777-779. DOI: 10.1039/B713951A
  146. 146. Higashi S, Takenaka H, Ito Y, Oe Y, Ohta T. Synthesis of RuCl2(xantphos)​L (L = PPh3, P(OPh)​3, DMSO) complexes, and their catalytic activity for the addition of carboxylic acids onto olefins. Journal of Organometallic Chemistry. 2015;791:46-50. DOI: 10.1016/j.jorganchem.2015.04.016
  147. 147. Rosenfeld C D, Shekhar S, Takemiya A, Utsunomiya M, Hartwig JF. Hydroamination and hydroalkoxylation catalyzed by triflic acid. Parallels to reactions initiated with metal triflates. Organic Letters. 2006;8:4179-4182. DOI: 10.1021/ol061174+
  148. 148. Li Z, Zhang J, Brouwer C, Yang C, Reich WN, He C. Brønsted acid catalyzed addition of phenols, carboxylic acids, and tosylamides to simple olefins. Brønsted acid catalyzed addition of phenols, carboxylic acids, and tosylamides to simple olefins. Organic Letters. 2006;8:4175-4178. DOI: 10.1021/ol0610035
  149. 149. Perkowski JA, Nicewicz AD. Direct catalytic anti-Markovnikov addition of carboxylic acids to alkenes. Journal of the American Chemical Society. 2013;135:10334-10337. DOI: 10.1021/ja4057294

Written By

Kouichi Matsumoto, Rina Yanagi and Yohei Oe

Submitted: 04 June 2017 Reviewed: 26 January 2018 Published: 13 June 2018

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution 3.0 License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Continue reading from the same book

View All
Chapter 3 Applications of Carboxylic Acids in Organic Synthe...

By Aidé Sáenz-Galindo, Lluvia I. López-López, Fabiola...

2451 downloads

Chapter 4 The Excretion of Di- and Tricarboxylic Acids by Ro...

By Jörg Gerke

1200 downloads

Chapter 5 Isolation and GC Analysis of Fatty Acids: Study Ca...

By Saša Đurović, Saša Šorgić, Saša Popov, Marija Rado...

1273 downloads