5873-86-9Relevant academic research and scientific papers
Base-Catalyzed Transesterification of Thionoesters
Newton, Josiah J.,Britton, Robert,Friesen, Chadron M.
, p. 12784 - 12792 (2018/10/20)
Here we report a convenient synthesis of thionoesters by base-catalyzed transesterification. Benzyl and alkyl thionobenzoates and thionoheterobenzoates were efficiently prepared using various alcohols catalyzed by the corresponding sodium alkoxide. This methodology features a broad substrate scope, good to excellent yields, short reaction times, while simultaneously driving the reaction toward completion through the removal of the methanol byproduct. We also report the conversion of a small collection of thionobenzoates into the corresponding α,α-difluorobenzyl ethers to demonstrate the conversion of alcohols into difluorobenzyl or difluoroheterobenzyl ethers, a process that could prove useful for lead optimization in medicinal chemistry.
An Expeditious Route to trans-Configured Tetrahydrothiophenes Enabled by Fe(OTf)3-Catalyzed [3+2] Cycloaddition of Donor–Acceptor Cyclopropanes with Thionoesters
Matsumoto, Yohei,Nakatake, Daiki,Yazaki, Ryo,Ohshima, Takashi
supporting information, p. 6062 - 6066 (2018/03/28)
A synthetic route to trans-configured tetrahydrothiophenes (THTs) through Fe(OTf)3-promoted [3+2] cycloaddition of donor–acceptor cyclopropanes with thionoesters was developed. The cycloaddition proceeded in high yield with high diastereoselectivity, affording transient α-alkoxy THTs. Not only aromatic and aliphatic thionoesters, but also thionolactone were applicable to the present iron catalysis. Further transformation of the S,O-ketal functionality of the product was achieved in a highly trans diastereoselective manner. Moreover, the utility of our methodology was clearly demonstrated by the synthesis of enantioenriched trans-configured THTs.
Facile Synthesis of 2,5-Disubstituted Thiazoles from Terminal Alkynes, Sulfonyl Azides, and Thionoesters
Miura, Tomoya,Funakoshi, Yuuta,Fujimoto, Yoshikazu,Nakahashi, Junki,Murakami, Masahiro
supporting information, p. 2454 - 2457 (2015/05/27)
A sequential procedure for the synthesis of 2,5-disubstituted thiazoles from terminal alkynes, sulfonyl azides, and thionoesters is reported. A copper(I)-catalyzed 1,3-dipolar cycloaddition of terminal alkynes with sulfonyl azides affords 1-sulfonyl-1,2,3-triazoles, which then react with thionoesters in the presence of a rhodium(II) catalyst. The resulting 3-sulfonyl-4-thiazolines subsequently aromatize into the corresponding 2,5-disubstituted thiazoles by elimination of the sulfonyl group. (Chemical Equation Presented).
Aromatic selenoic,selenothioic,and diselenoic acid salts:isolation, characterization, and 77senmr spectra,together with theoretical elucidation
Murai, Toshiaki,Nishi, Daisuke,Hayashi, Satoko,Nakanishi, Waro
supporting information, p. 677 - 692 (2014/07/08)
To systematically elucidate molecular and electronic structures of aromatic selenoic acid salts and their heavier congeners, they were synthesized by reacting selenoic, selenothioic, and diselenoic acid Se-[2-(trimethylsilyl) ethyl] esters with ammonium f
Methanolysis of thioamide promoted by a simple palladacycle is accelerated by 108 over the methoxide-catalyzed reaction
Liu, C. Tony,Maxwell, Christopher I.,Pipe, Stephanie G.,Neverov, Alexei A.,Mosey, Nicholas J.,Brown, R. Stan
supporting information; experimental part, p. 20068 - 20071 (2012/02/02)
Palladacycle 1 catalyzes the methanolytic cleavage of N-methyl-N-(4- nitrophenyl)thiobenzamide (4) via a mechanism involving formation of a Pd-bound tetrahedral intermediate (TI). The rate constant for decomposition of the complex formed between 1, methox
P4S10/dimethicone tandem: Efficient reagent for thionation of various aromatic amides and esters
Cho, Dongho,Ahn, Jiyoung,De Castro, Kathlia A.,Ahn, Hyunseok,Rhee, Hakjune
supporting information; experimental part, p. 5583 - 5588 (2010/10/02)
Organosulfur compounds are valuable because of their rich and varied chemistry especially in biological field. We report a new and efficient way for thionation of various aromatic amides and esters using P4S 10/ dimethicone tandem. The ease of handling and higher yield makes this protocol economical.
Disparate behavior of carbonyl and thiocarbonyl compounds: Acyl chlorides vs thiocarbonyl chlorides and isocyanates vs isothiocyanates
Wiberg, Kenneth B.,Wang, Yi-Gui,Miller, Scott J.,Puchlopek, Angela L. A.,Bailey, William F.,Fair, Justin D.
experimental part, p. 3659 - 3664 (2009/09/26)
(Figure Presented) The reaction of benzoyl chloride with methanol catalyzed by pyridine is 9 times more rapid than is the same reaction with thiobenzoyl chloride. The difference in reactivity, as well as the dealkylation reactions that occur when the reaction of thiobenzoyl chloride is catalyzed by bases such as Et3N, can be understood in terms of the charge distributions in the intermediate acylammonium ions. The reaction of PhNCO with ethanol occurs at a much higher rate (4.8 × 104) than that of PhNCS, corresponding to a difference in activation free energies for the additions of 6 kcal/mol. Transition states for each of these reactions were located, and each involves two alcohol molecules in a hydrogen bonded six-membered ring arrangement. Information concerning differences in reactivity was derived from analysis of Hirshfeld atomic charge distributions and calculated hydrogenolysis reaction energies.
Facile conversion of dithioesters into carboxylic acids or esters using alkaline hydrogen peroxide
Grellepois, Fabienne,Portella, Charles
experimental part, p. 3443 - 3446 (2009/05/09)
Simple, mild, and environmentally friendly procedures for the direct conversion of dithioesters into either carboxylic acids or esters using hydrogen peroxide under alkaline conditions are described. Georg Thieme Verlag.
2,4-Disubstituted-5-acetoxythiazoles: useful intermediates for the synthesis of thiazolones and 2,4,5-trisubstituted thiazoles
Qiao,Dominique,Goodnow Jr.
, p. 3682 - 3686 (2008/09/20)
A variety of 2,4-disubstituted-5-acetoxythiazoles were prepared from the substituted methyl benzoates in good to moderate yields using a three-step sequence: (1) ester to thionoester conversion, (2) coupling with an amino acid, and (3) acetic anhydride me
Thionation of esters and lactones with the reagent combination of phosphorus pentasulfide and hexamethyldisiloxane
Curphey, Thomas J
, p. 371 - 373 (2007/10/03)
The combination of P4S10 and hexamethyldisiloxane converts esters and lactones to thionoesters and thionolactones in yields comparable to or superior to those obtained with Lawesson's reagent. The method has the advantage that reagent-derived byproducts may be removed by a simple hydrolytic workup or by filtration through silica gel, rather than by chromatography, as required for Lawesson's reagent.
