20278-32-4Relevant academic research and scientific papers
Fe3O4@GlcA@Cu-MOF: A Magnetic Metal-Organic Framework as a Recoverable Catalyst for the Hydration of Nitriles and Reduction of Isothiocyanates, Isocyanates, and Isocyanides
Ghorbani-Choghamarani, Arash,Taherinia, Zahra
supporting information, p. 902 - 909 (2020/11/30)
A novel magnetic metal-organic framework (Fe3O4@GlcA@Cu-MOF) has been prepared and characterized by spectroscopic, microscopic, and magnetic techniques. This magnetically separable catalyst exhibited high catalytic activity for nitrile hydration and the ability to reduce isothiocyanates, isocyanates, and isocyanides with excellent activity and selectivity without any additional reducing agent.
Chemoselective reduction of isothiocyanates to thioformamides mediated by the Schwartz reagent
De La Vega-Hernández, Karen,Senatore, Raffaele,Miele, Margherita,Urban, Ernst,Holzer, Wolfgang,Pace, Vittorio
supporting information, p. 1970 - 1978 (2019/02/20)
Thioformamides are easily prepared-under full chemocontrol-through the partial reduction of isothiocyanates with the in situ generated Schwartz reagent. The high electrophilicity of the starting materials enables the straightforward addition of the hydride ion, thus constituting a reliable and high-yielding method for obtaining variously functionalized thioformamides. Sensitive chemical groups to the reduction conditions such as nitro, ester, alkene, azo, azide and keto groups do not interfere with the chemoselectivity of the process. Moreover, the stereochemical information embodied in the starting material is fully retained in the final products. The synthetic potential of the selected thioformamide template is also briefly discussed.
Copper-catalyzed chemoselective cross-coupling reaction of thioamides and α-diazocarbonyl compounds: Synthesis of enaminones
Pal, Arpal,Koduri, Naga D.,Wang, Zhiguo,Quiroz, Erika Lopez,Chong, Alexandra,Vuong, Matthew,Rajagopal, Nisha,Nguyen, Michael,Roberts, Kenneth P.,Hussaini, Syed R.
supporting information, p. 586 - 589 (2017/01/16)
The development of operationally simple and cost-effective methods for C[sbnd]C bond formation reactions are highly important in pharmaceutical, agrochemical and material research. In this article we describe the first copper-catalyzed cross-coupling reaction of thioamides with acceptor/acceptor-substituted and acceptor-only substituted α-diazocarbonyl compounds to yield enaminones. The reaction shows broad substrate scope in terms of thioamides and diazocarbonyl compounds. Primary, secondary and tertiary thioamides all give enanminones when reacted with α-diazodiesters, α-diazoketoesters, α-diazodiketones, α-diazoketoamides, α-diazoesteramides, α-diazoketosulfones and α-diazomonoketones.
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.
Environmentally green synthesis of thioformamide derivatives
Ramazani, Ali,Joo, Sang Woo,Nasrabadi, Fatemeh Zeinali
, p. 405 - 412 (2013/07/26)
Reactions of isocyanides with thioacids in water proceeded smoothly at room temperature and in neutral conditions to afford thioformylamide and thioformamide derivatives in high yields. The reaction proceeded smoothly and cleanly under mild conditions and
Microwave-assisted synthesis of substituted 1,2,4-triazoles
Wu, Dong-Qing,He, Jian- Li,Wang, Jun-Ke,Wang, Xi-Cun,Zong, Ying-Xiao
, p. 293 - 294 (2007/10/03)
An efficient synthesis of substituted 1,2,4-triazoles has been extended, utilising a wide range of N-substituted amides and hydrazides.
Novel reduction of isothiocyanates to thioformamides with SmI2 and tert-butyl alcohol in the presence of HMPA
Park, Heui Sul,Lee, In Sang,Kim, Yong Hae
, p. 1805 - 1806 (2007/10/03)
Isocyanates react with SmI2 and tert-butyl alcohol in the presence of HMPA to give thioformamides in excellent yields under mild conditions.
Approaches to Chemically Modified Enzymes As Synthetic Catalysts
Aitken, David J.,Alijah, Renate,Onyiriuka, Samuel O.,Suckling, Colin J.,Wood, Hamish C. S.,Zhu, Limin
, p. 597 - 608 (2007/10/02)
Attempts to introduce new catalytic activities of potential use in synthetic transformations into enzyme active sites are described.Substitution of the naturally occurring zinc in carboxypeptidase A by several metals known to catalyse hydrogenation was investigated; a new protein characterised as a rhodium carboxypeptidase was isolated but it failed to show activity as a hydrogenation catalyst for the reduction of a series of dehydroamino acid amides.Horse liver alcohol dehydrogenase was investigated for its potential to act as an oxygen transferase via Lewis acid catalysis.A series of cyclohexenyl and phenylribosides together with new alkenyl(arenyl)oxymethylenoxyethanols was prepared for evaluation as substrates; in the course of this study, novel neighbouring group participation by the oxygen atom of a chloromethyl ether was observed.Although the binding of potential oxygen acceptors (alkenes and aromatic compounds) and oxygen donors (hydrogen peroxide and alkyl hydroperoxides) was demonstrated, oxygen transfer did not occur with the combinations investigated.In contrast to the failure of the above metalloenzymes to catalyse new reactions, papain modified at the active site sulfhydryl group by thiazolium salts and pyridinium salts was shown to exhibit reactions characteristic of the covalently attached cofactor.Thus the thiazolopapains acted as decarboxylation catalysts for pyruvate and the pyridinopapains could be reduced to dihydropyridines which reduced electrophilic carbonyl substrates with small enantiomeric excess.
