74112-36-0Relevant academic research and scientific papers
Tropolonate salts as acyl-transfer catalysts under thermal and photochemical conditions: Reaction scope and mechanistic insights
Mai, Binh Khanh,Koenigs, Rene M.,Nguyen, Thanh Vinh,Lyons, Demelza J.M.,Empel, Claire,Pace, Domenic P.,Dinh, An H.
, p. 12596 - 12606 (2020/11/18)
Acyl-transfer catalysis is a frequently used tool to promote the formation of carboxylic acid derivatives, which are important synthetic precursors and target compounds in organic synthesis. However, there have been only a few structural motifs known to efficiently catalyze the acyl-transfer reaction. Herein, we introduce a different acyl-transfer catalytic paradigm based on the tropolone framework. We show that tropolonate salts, due to their strong nucleophilicity and photochemical activity, can promote the coupling reaction between alcohols and carboxylic acid anhydrides or chlorides to give products under thermal or blue light photochemical conditions. Kinetic studies and density functional theory calculations suggest interesting mechanistic insights for reactions promoted by this acyl-transfer catalytic system.
Consecutive addition esterification and hydrolysis of cyclic olefins catalyzed by multi-SO3H functionalized multi heteropolyanion-based ionic hybrids undersolvent-free conditions
Zheng, Guocai,Li, Xinzhong
, p. 933 - 941 (2019/03/17)
An efficient protocol for the synthesis of cycloalkyl carboxylates and alcohols from cyclic olefins is described. The cyclic olefins were converted to corresponding target molecules under solvent-free conditions catalyzed by two novel multi-SO3H functionalized multi heteropolyanion-based ionic hybrids through one-pot consecutive addition esterification and hydrolysis reactions. This approach has several advantages, including high yield, simple workup and simple purification.
CO2-expanded bio-based liquids as novel solvents for enantioselective biocatalysis
Hoang, Hai Nam,Nagashima, Yoshihiro,Mori, Shuichi,Kagechika, Hiroyuki,Matsuda, Tomoko
, p. 2984 - 2989 (2017/04/26)
For the first time, CO2-expanded bio-based liquids were reported as novel and sustainable solvents for biocatalysis. Herein, it was found that by expansion with CO2, 2-methyltetrahydrofuran (MeTHF), and other bio-based liquids, which were not favorable solvents for immobilized Candida antarctica lipase B (Novozym 435) catalyzed transesterification, were tuned into excellent reaction media. Especially, for the kinetic resolution of challenging bulky secondary substrates such as rac-1-adamantylethanol, the lipase displayed very high activity with excellent enantioselectivity (E value > 200) in CO2-expanded MeTHF (MeTHF concentration 10% v/v, 6 MPa), whereas there was almost no activity observed in conventional organic solvents.
Enzymatic kinetic resolution of aliphatic sec-alcohols by LipG9, a metagenomic lipase
Bandeira, Pamela T.,Alnoch, Robson C.,De Oliveira, Alfredo R.M.,De Souza, Emanuel M.,De O.P., Fábio,Krieger, Nadia,Piovan, Leandro
, p. 58 - 63 (2016/01/30)
Bioprospection for new enantioselective enzymes for application in organic synthesis is a prominent area of investigation in biocatalysis. In this context, here we present the evaluation of an immobilized lipase isolated from a metagenomic library (LipG9) for the enzymatic kinetic resolution (EKR) of aliphatic sec-alcohols, which are still challenging substrates, since low enantioselectivity values are usually observed for these resolutions. LipG9 was successfully employed in EKR of aliphatic alcohols, which were resolved with satisfactory conversions (19-59%) and enantiomeric excesses for alcohols (26-88%) and esters (30-96%) by transesterification reactions, demonstrating that its performance is equal to or better than commercially available enzymes for the same reaction.
Graphite oxide-catalyzed acetylation of alcohols and phenols
Liu, Yuan-Yuan,Qi, Jun-Mei,Bai, Li-Sha,Xu, Yue-Long,Ma, Ning,Sun, Fei-Fei
supporting information, p. 726 - 730 (2016/05/19)
Graphite oxide (GO) was used as a catalyst for the reactions of alcohols and phenols with acetic anhydride. The acetates of primary and secondary alcohols were prepared in good to excellent yields in short reaction time under mild conditions. Electron deficient phenols could be converted to the corresponding acetates steadily. As an efficient catalyst, GO is easily available, cheap, moderately toxic and weakly acidic.
Asymmetric hydrogenation of allylic alcohols using ir?N,P-Complexes
Li, Jia-Qi,Liu, Jianguo,Krajangsri, Suppachai,Chumnanvej, Napasawan,Singh, Thishana,Andersson, Pher G.
, p. 8342 - 8349 (2018/05/23)
In this study, a series of γ,γ-disubstituted and β,γ-disubstituted allylic alcohols were prepared and successfully hydrogenated using suitable N,P-based Ir complexes. High yields and excellent enantioselectivities were obtained for most of the substrates studied. This investigation also revealed the effect of the acidity of the N,P?Ir-complexes on the acid-sensitive allylic alcohols. DFT ΔpKa calculations were used to explain the effect of the N,P-ligand on the acidity of the corresponding Ir-complex. The selectivity model of the reaction was used to accurately predict the absolute configuration of the hydrogenated alcohols.
Sulfonic acid-functionalized periodic mesoporous organosilicas in esterification and selective acylation reactions
Karimi, Babak,Mirzaei, Hamid M.,Mobaraki, Akbar,Vali, Hojatollah
, p. 3624 - 3631 (2015/07/01)
The application of sulfonic acid-functionalized periodic mesoporous organosilicas (PMOs) having either phenyl (1a) or ethyl (1b) bridging groups was investigated in the esterification of a variety of alcohols and fatty acids. It was found that 1b consistently exhibited higher catalytic performance than 1a in the described reaction. In particular, it was proposed that the superior catalytic activity of 1b in esterification of fatty acids with methanol is a result of adequate hydrophobic-hydrophilic surface balance in the ethyl PMO catalyst. In addition, the study of chemoselective acylation of 1,3-butanediol with dodecanoic acid with varied mesoporous silica-supported solid sulfonic acids including both 1a and 1b implies that there is a compromise between the reaction selectivity and the surface physicochemical properties of the employed catalyst. Our results clearly show that the catalyst having high surface hydrophilic nature gives high selectivity toward the formation of mono-acylated products whereas those with relatively high hydrophobic characteristics showed enhanced selectivity toward the formation of di-acylated products.
Synthesis of sulfonic acid containing ionic-liquid-based periodic mesoporous organosilica and study of its catalytic performance in the esterification of carboxylic acids
Elhamifar, Dawood,Karimi, Babak,Moradi, Abbas,Rastegar, Javad
, p. 1147 - 1152 (2014/10/16)
A new sulfonic acid containing ionic-liquid-based periodic mesoporous organosilica (PMO-IL-SO3H) material was prepared and its catalytic application was investigated in the esterification of carboxylic acids with alcohols. The PMO-IL-SO3H nanocatalyst was first characterized with diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and nitrogen sorption analysis. Then, the catalytic performance of this material was studied in the esterification of carboxylic acids with short- and long-chain aliphatic alcohols, cyclic alcohols, and benzylic alcohols under solvent-free conditions. The results showed that the catalyst has superior activity for the conversion of several alcohols to afford the corresponding ester products in excellent yields and high purity. Moreover, the catalyst could be recovered and reused several times without a significant decrease in activity and product selectivity. Copyright
Silica-supported boric acid catalyzed synthesis of dihydropyrimidin-2-ones, bis(indolyl)methanes, esters and amides
Kumar, Vishal,Singh, Chitra,Sharma, Upendra,Verma, Praveen K.,Singh, Bikram,Kumar, Neeraj
, p. 83 - 89 (2014/02/14)
Silica-supported boric acid (H3BO3-SiO2) has been established as a green, efficient and recyclable catalyst for the synthesis of dihydropyrimidin-2-ones, bis(indolyl)methanes, and acetylation of alcohols, phenols, amines and thiols under solvent free conditions. The main features of the present method include clean reaction, mild conditions, low loading of environment friendly catalyst and easy workup procedure. The catalyst can be recycled at least five times without any significant loss in activity.
Direct dehydrative esterification of alcohols and carboxylic acids with a macroporous polymeric acid catalyst
Minakawa, Maki,Baek, Heeyoel,Yamada, Yoichi M. A.,Han, Jin Wook,Uozumi, Yasuhiro
supporting information, p. 5798 - 5801 (2013/12/04)
A macroporous polymeric acid catalyst was prepared for the direct esterification of carboxylic acids and alcohols that proceeded at 50-80 C without removal of water to give the corresponding esters with high yield. Flow esterification for the synthesis of biodiesel fuel was also achieved by using a column-packed macroporous acid catalyst under mild conditions without removal of water.
