23522-73-8Relevant academic research and scientific papers
Environmentally benign decarboxylative: N-, O-, and S-Acetylations and acylations
Ghosh, Santanu,Purkait, Anisha,Jana, Chandan K.
supporting information, p. 8721 - 8727 (2020/12/30)
An operationally simple and general method for acetylation and acylation of a wide variety of substrates (amines, alcohols, phenols, thiols, and hydrazones) has been reported. Meldrum's acid and its derivatives have been used as an air-stable, non-volatile, cost-effective, and easy to handle acetylating/acylating agent. Easily separable byproducts (CO2 and acetone) allowed the isolation of analytically pure acetylated products without the requirement of work-up and any chromatography. This journal is
Indium-Catalyzed Reductive Sulfidation of Esters by Using Thiols: An Approach to the Diverse Synthesis of Sulfides
Miyazaki, Takahiro,Kasai, Shinsei,Ogiwara, Yohei,Sakai, Norio
supporting information, p. 1043 - 1049 (2016/03/01)
A new reductive preparation of unsymmetrical sulfides from esters and thiols in the presence of InI3 and either 1,1,3,3-tetramethyldisiloxane (TMDS) or PhSiH3 as the reductant was developed. This protocol was applied to not only benzoic acid esters that have a methoxy, methyl, chloro, bromo, iodo, or trifluoromethyl group on the aromatic ring but also aliphatic acid esters with either aromatic or aliphatic thiols. A reaction mechanism is proposed by using Hammett plot results and several control experiments. The reductive preparation of unsymmetrical sulfides from esters and thiols by using InI3 and either 1,1,3,3-tetramethyldisiloxane (TMDS) or PhSiH3 was developed. Several mechanistic studies support that the present transformation proceeds through O,S-and S,S-acetals as the reaction intermediates. TMDS = 1,1,3,3-tetramethyldisiloxane, R = aliphatic group.
Fe-catalyzed thioesterification of carboxylic esters
Magens, Silja,Plietker, Bernd
supporting information; experimental part, p. 8807 - 8809 (2011/09/16)
Second nature: Starting from shelf-stable aryl esters and thiols, a variety of carboxylic acid esters were transformed into the corresponding thioesters with no racemization of labile stereocenters (see scheme). The method was successfully applied in a native chemical-ligation-type peptide formation, which suggests that the thiol may act as a co-catalyst for future 1,2-additions of pronucleophiles to carboxylic esters.
Nucleophilic iron catalysis in transesterifications: Scope and limitations
Magens, Silja,Plietker, Bernd
supporting information; experimental part, p. 3715 - 3721 (2010/08/07)
Figure presented The ester bond is one of the most common structural motifs found in nature. Apart from the condensation between an acid and an alcohol, transesterifications represent another mechanistic alternative for the preparation of this compound class. The present paper summarizes our most recent investigations in this field, using nucleophilic iron complexes as catalysts for transesterifications under neutral conditions. This new type of metal catalyst complements the existing methodologies, which rely on Lewis acidic metal complexes. Investigations on scope and limitations, stereochemical course, and chemoselectivities will be presented.
Reaction of dicarbonates with carboxylic acids catalyzed by weak Lewis acids: General method for the synthesis of anhydrides and esters
Bartoli, Giuseppe,Bosco, Marcella,Carlone, Armando,Dalpozzo, Renato,Marcantoni, Enrico,Melchiorre, Paolo,Sambri, Letizia
, p. 3489 - 3496 (2008/09/19)
The reaction between carboxylic acids (RCOOH) and dialkyl dicarbonates [(R1OCO)2O], in the presence of a weak Lewis acid such as magnesium chloride and the corresponding alcohol (R1OH) as the solvent, leads to the esters RCOOR1 in excellent yields. The mechanism involves a double addition of the acid to the dicarbonate, affording a carboxylic anhydride [(RCO)2O], R1OH and carbon dioxide. The esters arise from the attack of the alcohols on the anhydrides. Exploiting the lesser reactivity of tert-butyl alcohol in comparison with other alcohols, a clean synthesis of both carboxylic anhydrides and esters has been set up. In the former reaction, an acid/Boc2O molecular ratio of 2:1 leads to the anhydride in good to excellent yields, depending on the stability of the resulting anhydride to the usual workup conditions. In the latter reaction, stoichiometric mixtures of the acid and Boc2O are allowed to react with a twofold excess of a primary alcohol, secondary alcohol or phenol (R 2OH) to give the corresponding esters (RCOOR2). Purification of the products is particularly easy since all byproducts are volatile or water soluble. A very easy chromatography is required only in the case of nonvolatile alcohols. A broad variety of sensitive functional groups is tolerated on both the acid and the alcohol, in particular a high chemoselectivity is observed. In fact, no transesterification processes occur with the acid-sensitive acetoxy group and methyl esters. Georg Thieme Verlag Stuttgart.
A New and Efficient Esterification Reaction via Mixed Anhydrides by the Promotion of a Catalytic Amount of Lewis Acid
Miyashita, Mitsutomo,Shiina, Isamu,Miyoshi, So,Mukaiyama, Teruaki
, p. 1516 - 1527 (2007/10/02)
In the presence of a catalytic amount of Lewis acid, various carboxylic esters or S-phenyl carbothioates are prepared in excellent yields by the respective reactions of equimolar amounts of silyl carboxylates and alkyl silyl ethers or phenyl silyl sulfides with 4-trifluoromethylbenzoic anhydride.
A New and Efficient Method for the Preparation of S-Phenyl Carbothioates via Mixed Anhydrides Using Active Titanium(IV) Salts
Mukaiyama, Teruaki,Miyashita, Mitsutomo,Shiina,, Isamu
, p. 1747 - 1750 (2007/10/02)
In the presence of a catalytic amount of titanium(IV) salt, various S-phenyl carbothioates are prepared in excallent yields by the reaction of nearly equimolar amounts of silyl derivatives of carboxylic acids and benzenethiols with p-trifluoromethylbenzoic anhydride.
