359803-67-1Relevant academic research and scientific papers
Esterification of Tertiary Amides: Remarkable Additive Effects of Potassium Alkoxides for Generating Hetero Manganese–Potassium Dinuclear Active Species
Akiyama, Shoko,Himo, Fahmi,Hirai, Takahiro,Katayama, Shoichiro,Kato, Daiki,Mai, Binh Khanh,Mashima, Kazushi,Nagae, Haruki
supporting information, (2020/07/25)
A catalyst system of mononuclear manganese precursor 3 combined with potassium alkoxide served as a superior catalyst compared with our previously reported manganese homodinuclear catalyst 2 a for esterification of not only tertiary aryl amides, but also tertiary aliphatic amides. On the basis of stoichiometric reactions of 3 and potassium alkoxide salt, kinetic studies, and density functional theory (DFT) calculations, we clarified a plausible reaction mechanism in which in situ generated manganese–potassium heterodinuclear species cooperatively activates the carbonyl moiety of the amide and the OH moiety of the alcohols. We also revealed details of the reaction mechanism of our previous manganese homodinuclear system 2 a, and we found that the activation free energy (ΔG≠) for the manganese–potassium heterodinuclear complex catalyzed esterification of amides is lower than that for the manganese homodinuclear system, which was consistent with the experimental results. We further applied our catalyst system to deprotect the acetyl moiety of primary and secondary amines.
A Straightforward Conversion of Activated Amides and Haloalkanes into Esters under Transition-Metal-Free Cs 2 CO 3 /DMAP Conditions
Chen, Liuqing,Gu, Ying,Jian, Junsheng,Liu, Yueping,Miao, Liqiong,Wang, Zijia,Zeng, Zhuo
, p. 4078 - 4084 (2019/10/28)
The esterification of activated amides, N -acylsaccharins, under transition-metal-free conditions with good functional group tolerance has been developed, resulting in C-N cleavage leading to efficient synthesis of a variety of esters in moderate to good yields. This work demonstrates that esterification may proceed by using simple N -acylsaccharins, haloalkanes, and Cs 2 CO 3 as oxygen source.
Synthesis of Esters from Stable and Convenient Sulfoxonium Precursors under Catalyst- And Additive-Free Conditions
Wu, Xiao-Feng,Yuan, Yang
, p. 1820 - 1824 (2019/09/09)
A convenient and efficient procedure for the construction of esters from stable sulfoxonium ylides and alcohols has been developed. This protocol presents a broad substrate scope and good yields of the desired esters can be isolated. Notably, no catalyst, oxidant, base or any other additive is required.
Dinuclear manganese alkoxide complexes as catalysts for C-N bond cleavage of simple tertiary: N, N -dialkylamides to give esters
Nagae, Haruki,Hirai, Takahiro,Kato, Daiki,Soma, Shusei,Akebi, Shin-Ya,Mashima, Kazushi
, p. 2860 - 2868 (2019/03/13)
Amide bonds are stable due to the resonance between the nitrogen lone pair and the carbonyl moiety, and therefore the chemical transformation of amides, especially tertiary amides, involving C-N bond fission is considered one of the most difficult organic reactions, unavoidably requiring harsh reaction conditions and strong acids or bases. We report the catalytic C-N bond cleavage of simple tertiary N,N-dialkylamides to give corresponding esters using a catalyst system (2 mol% based on Mn atoms) of a tetranuclear manganese alkoxide, [Mn(acac)(OEt)(EtOH)]4 (1c), combined with four equivalents of 4,7-bis(dimethylamino)-1,10-phenanthroline (L1: Me2N-Phen). Regarding the reaction mechanism, we isolated a dinuclear manganese complex, [Mn(acac)(OEt)(Phen)]2 (6c), which was revealed as the catalytically active species for the esterification of tertiary amides.
Dehydrogenative cross-coupling of primary alcohols to form cross-esters catalyzed by a manganese pincer complex
Das, Uttam Kumar,Ben-David, Yehoshoa,Leitus, Gregory,Diskin-Posner, Yael,Milstein, David
, p. 479 - 484 (2019/01/11)
Base-metal-catalyzed dehydrogenative cross-coupling of primary alcohols to form cross-esters as major products, liberating hydrogen gas, is reported. The reaction is catalyzed by a pincer complex of earth-abundant manganese in the presence of catalytic base, without any hydrogen acceptor or oxidant. Mechanistic insight indicates that a dearomatized complex is the actual catalyst, and indeed this independently prepared dearomatized complex catalyzes the reaction under neutral conditions.
Practical: In situ -generation of phosphinite ligands for palladium-catalyzed carbonylation of (hetero)aryl bromides forming esters
Wang, Lin,Neumann, Helfried,Spannenberg, Anke,Beller, Matthias
supporting information, p. 7469 - 7472 (2017/07/12)
An effective method for alkoxycarbonylation of (hetero)aryl bromides is developed in the presence of in situ-generated phosphinite ligands tBu2POR (R = nBu, nPr, Et or Me). For this purpose commercially available tBu2PCl was used as the pre-ligand in the presence of different alcohols. For the first time cross coupling reactions with two alcohols-one generating the ligand, the other used as substrate-were developed. Through this method, ligand optimization can be performed in a more efficient manner and the desired products could be obtained with good yields and selectivity.
Synthetic method of an ester compound
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Paragraph 0051; 0052; 0053, (2017/02/02)
The invention discloses a synthetic method of an ester compound and belongs to the technical field of organic synthesis. The synthetic method includes the steps of: dissolving an aldehyde compound (1) and a halogenated hydrocarbon compound (2) in a solvent, adding an oxidant and a catalyst, and performing a reaction at 60-100 DEG C to obtain the target product ester compound (3). A reaction equation of the synthetic method is represented as follows. The method, compared with the prior art, has the following advantages: 1) the raw materials are easy to obtain and are low in cost; 2) the reaction conditions are mild, operations are simple, and reaction time is short; and 3) a substrate has wide available range and can be used for synthesis of various ester compounds.
Fe-Catalyzed Aerobic Oxidative C-CN Bond Cleavage of Arylacetonitriles Leading to Various Esters
Kong, Weiguang,Li, Bingnan,Xu, Xuezhao,Song, Qiuling
, p. 8436 - 8443 (2016/09/28)
Fe-catalyzed aerobic oxidative esterifications of arylacetonitriles with alcohols, tri alkoxsilanes, silicate esters, or borate esters have been developed. The acyl groups which were in situ generated via chemoselective C(CO)-CN bond cleavage were directly used as electrophiles, leading to corresponding aryl esters in good to excellent yields under molecular oxygen when attacked by alcohols or alcohol surrogates. Dioxygen serves as both oxidant and reactant in this protocol. The reaction has a very broad substrate scope. Cheap starting materials as well as environmentally benign and inexpensive iron catalyst and ideal oxidant O2 feature this transformation and make it a practical and sustainable protocol to afford esters.
A facile, one-pot procedure for the conversion of aromatic aldehydes to esters, as well as thioesters and amides, via acyl hydrazide intermediates
Maruani, Antoine,Lee, Maximillian T. W.,Watkins, George,Akhbar, Ahmed R.,Baggs, Henry,Shamsabadi, André,Richards, Daniel A.,Chudasama, Vijay
, p. 3372 - 3376 (2016/01/16)
Herein we present an efficient method for the synthesis of esters from aromatic aldehydes via readily accessible acyl hydrazides. The developed reaction protocol is shown to be tolerant of a range of aromatic aldehydes, bearing various functionalities, as well as being amenable to the synthesis of thioesters and amides.
Nickel-catalyzed dehydrogenative cross-coupling: Direct transformation of aldehydes into esters and amides
Whittaker, Aaron M.,Dong, Vy M.
supporting information, p. 1312 - 1315 (2015/01/30)
By exploring a new mode of nickel-catalyzed cross-coupling, a method to directly transform both aromatic and aliphatic aldehydes into either esters or amides has been developed. The success of this oxidative coupling depends on the appropriate choice of catalyst and organic oxidant, including the use of either α,α,α-trifluoroacetophenone or excess aldehyde. Mechanistic data that supports a catalytic cycle involving oxidative addition into the aldehyde C-H bond is also presented.
