14309-88-7Relevant academic research and scientific papers
Transamidation of thioacetamide catalyzed by SbCl3
Ojeda-Porras, Andrea,Gamba-Sánchez, Diego
, p. 4308 - 4311 (2015)
A transamidation reaction of thioacetamide with primary and secondary amines is described. The use of catalytic amounts of SbCl3 notably increases the yields and diminishes the reaction times. Typically, the amines should be aliphatic, but aromatic amines can be used as well, though with lower yields. This is one of the few examples where antimony has been used as a catalyst in organic reactions.
An Aluminum(III)-Catalyzed Thioamide-Aldehyde-Styrene Condensation: Direct Synthesis of Allylic Thioamide Derivatives
Xu, Bin,Zhong, Xue,Wang, Xi-Cun,Quan, Zheng-Jun
, p. 2237 - 2240 (2016)
An aluminum(III) triflate catalyzed three-component synthesis of allylic thioamide derivatives by condensation of a thioamide, paraformaldehyde and a styrene is reported.
O,O-Diethyl dithiophosphoric acid mediated direct synthesis of thioamides from aldehydes and ketones
Yadav, Arvind K.,Srivastava, Vishnu P.,Yadav, Lal Dhar S.
, p. 7113 - 7116 (2012)
A general and convenient method for a one-pot conversion of aldehydes and ketones into thioamides has been developed. The protocol involves oximation of aldehydes and ketones followed by deoxygenative thioamidation of oximes with O,O-diethyl dithiophosphoric acid which acts as an acid as well a source of sulfur. The method is operationally simple, high yielding, and also applicable to the conversion of amides and nitriles into the corresponding thioamides.
An Efficient Heterobimetallic Lanthanide Alkoxide Catalyst for Transamidation of Amides under Solvent-Free Conditions
Sheng, Hongting,Zeng, Ruijie,Wang, Wenjuan,Luo, Shuwen,Feng, Yan,Liu, Jing,Chen, Weijian,Zhu, Manzhou,Guo, Qingxiang
, p. 302 - 313 (2017/02/05)
A practical heterobimetallic lanthanide-catalyzed transamidation of primary, secondary and tertiary amides with aliphatic and aromatic amines has been developed. The methodology was also applied to the weakly reactive thioamides to demonstrate its versatility and wide substrate scope. The heterobimetallic lanthanide catalysts showed high catalytic activity and a wide scope of substrates with good to excellent yields under solvent-free conditions. Efficient activation of the transamidation can be realized by the above complexes acting as cooperative acid–base bifunctional catalysts, which are proposed to be responsible for the higher reactivity in comparison with simple monometallic catalysts. (Figure presented.).
A neodymium/sodium heteroatoms double-metal complex and its preparation and use
-
Paragraph 0023; 0024, (2018/11/04)
The invention discloses a neodymium/sodium mixed bimetal complex and a preparation method and application thereof. The molecular formula of the neodymium/sodium mixed bimetal complex is Nd2Na8(OCH2CH2NMe2)12(OH)2, and the complex contains a dual-core rare earth center. The neodymium/sodium mixed bimetal complex can be used for synthesizing thioamide compounds through a catalytic amide exchange reaction, the reaction conditions are moderate, operation is easy, and the consumption of catalysts is low.
Selective thioacylation of amines in water: A convenient preparation of secondary thioamides and thiazolines
Pathak, Uma,Bhattacharyya, Shubhankar,Mathur, Sweta
, p. 4484 - 4488 (2015/02/19)
Primary thioamides have been utilised directly in water, without any derivatisation, to selectively thioacylate primary amines. By employing 2-hydroxyethylamines, the reaction can be extended to the preparation of 2-thiazolines via formation of β-hydroxythioamides.
A Robust, Eco-Friendly Access to Secondary Thioamides through the Addition of Organolithium Reagents to Isothiocyanates in Cyclopentyl Methyl Ether (CPME)
Pace, Vittorio,Castoldi, Laura,Monticelli, Serena,Safranek, Sandra,Roller, Alexander,Langer, Thierry,Holzer, Wolfgang
supporting information, p. 18966 - 18970 (2016/01/26)
The nucleophilic addition of widely available and variously functionalized organolithium reagents to isothiocyanates represents a straightforward, high-yielding, one-pot method to access secondary thioamides. The simple reaction conditions required and the broad scope (>50 cases examples) makes it a robust and reliable method to access both simple and complex thioamides, including enantiopure ones. Noxious and unpleasant-smelling sulfurating agents, usually employed in the literature established methods, are avoided during the whole synthetic procedure thus, rendering the protocol highly attractive, also for sustainability aspects.
Steric and Electronic Effects in the Synthesis and Regioselective Hydrolysis of Unsymmetrical Imides
Shang, Jing,Pourvali, Aysa,Cochrane, James R.,Hutton, Craig A.
, p. 1854 - 1858 (2015/12/26)
The AgI-promoted coupling reaction of thioamides and carboxylic acids is shown to be a useful method for the generation of unsymmetrical imides. The reaction proceeds efficiently with unhindered and electron-rich or neutral coupling partners, but not with hindered thioamides (such as thiopivalamides) or electron deficient thioamides (such as trifluorothioacetamides). Intriguingly, thioformamides are also ineffective coupling partners, despite having minimal steric or electronic influence. Hindered carboxylic acid coupling partners (such as pivalic acid) are tolerated, but electron deficient acids, such as trifluoroacetic acid, are ineffective coupling partners. Furthermore, an interplay of both steric and electronic effects is observed in the subsequent hydrolysis of unsymmetrical imides. Imides with a dimethoxybenzoyl group give high regioselectivity upon hydrolysis, favouring cleavage of the distal acyl group. Imides with a p-nitrobenzoyl or pivaloyl group give reversed selectivity, favouring cleavage of the proximal acyl group.
A new method for peptide synthesis in the N→C direction: Amide assembly through silver-promoted reaction of thioamides
Pourvali, Aysa,Cochrane, James R.,Hutton, Craig A.
, p. 15963 - 15966 (2015/01/09)
The Ag(i)-promoted coupling of amino acids and peptides with amino ester thioamides generates peptide imides without epimerisation. The peptide imides undergo regioselective hydrolysis under mild conditions to generate native peptides. This method was employed to prepare the pentapeptide thymopentin in the N→C direction, in high yield and purity.
Reductive alkylation of thioamides with Grignard reagents in the presence of Ti(O i Pr)4: Insight and extension
Hermant, Fabien,Urbaska, Ewelina,Seizilles De Mazancourt, Sarah,Maubert, Thomas,Nicolas, Emmanuel,Six, Yvan
supporting information, p. 5643 - 5653 (2015/02/19)
The reductive alkylation of thioamides by Grignard reagents in the presence of Ti(OiPr)4 is the subject of a study involving 20 different substrates. The influence of various parameters has been evaluated, showing notably that the yields of this moderately efficient process can be improved in several cases by applying a slow addition of the Grignard reagent. The results presented in this contribution also provide new insight into the reactivity of the proposed key intermediates, namely, a metalated iminium species and, ultimately, an α-metalated amine. Interestingly, by control of the temperature and the amount of Grignard reagent engaged, the reaction can be directed toward the selective formation of the former titanium intermediate complex. This represents an extension of the original method, allowing the synthesis of various previously inaccessible substituted amines by subsequent addition of a nucleophilic reagent. This role can be played not only by organomagnesium compounds but also by alkyllithium reagents, alkyltitanium(IV) complexes, and lithium aluminum hydride. The properties of the α-metalated amine final intermediate have also been explored, demonstrating that this complex is a poor nucleophile but can act as a radical precursor, which is especially evidenced when the resulting radical species are stabilized. Overall, this chemistry thus proves unexpectedly rich and can plausibly lay the basis for the development of new applications in the future.
