6279-44-3Relevant articles and documents
Rhodium-catalyzed regioselective addition of thioacids to terminal allenes: Enantioselective access to branched allylic thioesters
Breit, B.,Ziyaei Halimehjani, A.
supporting information, p. 1704 - 1707 (2022/02/17)
Rhodium-catalyzed regio-and enantioselective hydrothiolation of terminal allenes with thioacids is reported for the atom-economic synthesis of chiral branched allylic thioesters. By using a rhodium(i) catalyst system, diversities of terminal allenes and thioacids afforded the corresponding branched thioesters in excellent regioselectivity, high yield, and good enantioselectivity. This method was also explored for Fmoc-protected aminothioacids for diastereoselective synthesis of the corresponding thioesters.
Atmospheric Oxygen Mediated Radical Hydrothiolation of Alkenes
McCourt, Ruairí O.,Scanlan, Eoin M.
supporting information, p. 15804 - 15810 (2020/10/26)
A mild, metal-free, atmospheric oxygen-mediated radical hydrothiolation of alkenes (and alkyne) is reported. A variety of sulfur containing motifs including alkanethiols, thiophenols and thioacids undergo an atmospheric oxygen-mediated radical hydrothiolation reaction with a plethora of alkenes in good yield with excellent functional group compatibility, typically with short reaction times to furnish a range of functionalized products. Biomolecules proved tolerant to the conditions and the procedure is robust and easily executable requiring no specialized equipment. Concise mechanistic studies confirm the process proceeds through radical intermediates in a thiol-ene reaction manifold. The methodology offers an efficient “green” approach for thiol-ene mediated “click” ligation and a milder alternative to thermally initiated hydrothiolation processes.
Diversity Oriented Clicking (DOC): Divergent Synthesis of SuFExable Pharmacophores from 2-Substituted-Alkynyl-1-Sulfonyl Fluoride (SASF) Hubs
Barrow, Andrew S.,Cheng, Yunfei,Gialelis, Timothy L.,Giel, Marie-Claire,Kitamura, Seiya,Li, Gencheng,Moses, John E.,Ottonello, Alessandra,Sharpless, K. Barry,Smedley, Christopher J.,Wolan, Dennis W.
supporting information, p. 12460 - 12469 (2020/06/10)
Diversity Oriented Clicking (DOC) is a unified click-approach for the modular synthesis of lead-like structures through application of the wide family of click transformations. DOC evolved from the concept of achieving “diversity with ease”, by combining classic C?C π-bond click chemistry with recent developments in connective SuFEx-technologies. We showcase 2-Substituted-Alkynyl-1-Sulfonyl Fluorides (SASFs) as a new class of connective hub in concert with a diverse selection of click-cycloaddition processes. Through the selective DOC of SASFs with a range of dipoles and cyclic dienes, we report a diverse click-library of 173 unique functional molecules in minimal synthetic steps. The SuFExable library comprises 10 discrete heterocyclic core structures derived from 1,3- and 1,5-dipoles; while reaction with cyclic dienes yields several three-dimensional bicyclic Diels–Alder adducts. Growing the library to 278 discrete compounds through late-stage modification was made possible through SuFEx click derivatization of the pendant sulfonyl fluoride group in 96 well-plates—demonstrating the versatility of the DOC approach for the rapid synthesis of diverse functional structures. Screening for function against MRSA (USA300) revealed several lead hits with improved activity over methicillin.
Controllable thioester-based hydrogen sulfide slow-releasing donors as cardioprotective agents
Yao, Hong,Luo, Shanshan,Liu, Junkai,Xie, Shaowen,Liu, Yanpeng,Xu, Jinyi,Zhu, Zheying,Xu, Shengtao
, p. 6193 - 6196 (2019/06/07)
Hydrogen sulfide (H2S) is an important signaling molecule with promising protective effects in many physiological and pathological processes. However, the study of H2S has been impeded by the lack of appropriate H2S donors that could mimic its slow-releasing process in vivo. Herein, we report the rational design, synthesis, and biological evaluation of a series of thioester-based H2S donors. These cysteine-activated H2S donors release H2S in a slow and controllable manner. Most of the donors comprising an allyl moiety showed significant cytoprotective effects in H9c2 cellular models of oxidative damage. The most potent donor 5e decreased the mitochondrial membrane potential (MMP) loss and lactate dehydrogenase (LDH) release in H2O2-stimulated H9c2 cells. More importantly, donor 5e exhibited a potent cardioprotective effect in an in vivo myocardial infarction (MI) mouse model by reducing myocardial infarct size and cardiomyocyte apoptosis. Taken together, our studies demonstrated that these new allyl thioesters are potential cardioprotective agents by releasing H2S.
Fast and highly chemoselective alkynylation of thiols with hypervalent iodine reagents enabled through a low energy barrier concerted mechanism
Frei, Reto,Wodrich, Matthew D.,Hari, Durga Prasad,Borin, Pierre-Antoine,Chauvier, Clment,Waser, Jrme
supporting information, p. 16563 - 16573 (2015/01/09)
Among all functional groups, alkynes occupy a privileged position in synthetic and medicinal chemistry, chemical biology, and materials science. Thioalkynes, in particular, are highly useful, as they combine the enhanced reactivity of the triple bond with a sulfur atom frequently encountered in bioactive compounds and materials. Nevertheless, general methods to access these compounds are lacking. In this article, we describe the mechanism and full scope of the alkynylation of thiols using ethynyl benziodoxolone (EBX) hypervalent iodine reagents. Computations led to the discovery of a new, three-atom concerted transition state with a very low energy barrier, which rationalizes the high reaction rate. On the basis of this result, the scope of the reaction was extended to the synthesis of aryl- and alkyl-substituted alkynes containing a broad range of functional groups. New sulfur nucleophiles such as thioglycosides, thioacids, and sodium hydrogen sulfide were also alkynylated successfully to lead to the most general and practical method yet reported for the synthesis of thioalkynes.
A facile synthesis of thioacids by hydrolysis of 1-(acylthio)ethaniminium chlorides
Toriyama, Masaharu,Kamijo, Haruo,Motohashi, Shigeyasu,Takido, Toshio,Itabashi, Kunio
, p. 1661 - 1665 (2007/10/03)
A facile method for the preparation of thioacids in moderate to good yields has been developed by hydrolysis of 1-(acylthio)ethaniminium chlorides under a liquid-liquid two phase system consisting of benzene and a sodium hydroxide aqueous solution at room temperature. We have achieved facile preparation of these compounds without use of toxic compounds such as hydrogen sulfide.
