38793-64-5Relevant academic research and scientific papers
Stable group 8 metal porphyrin mono- And bis(dialkylcarbene) complexes: Synthesis, characterization, and catalytic activity
Che, Chi-Ming,Huang, Jie-Sheng,Low, Kam-Hung,Wan, Qingyun,Wang, Hai-Xu,Zhang, Jun-Long,Zhou, Cong-Ying
, p. 2243 - 2259 (2020/03/11)
Alkyl-substituted carbene (CHR or CR2, R = alkyl) complexes have been extensively studied for alkylcarbene (CHR) ligands coordinated with high-valent early transition metal ions (a.k.a. Schrock carbenes or alkylidenes), yet dialkylcarbene (CR2) complexes remain less developed with bis(dialkylcarbene) species being little (if at all) explored. Herein, several group 8 metal porphyrin dialkylcarbene complexes, including Fe- and Ru-mono(dialkylcarbene) complexes [M(Por)(Ad)] (1a,b, M = Fe, Por = porphyrinato dianion, Ad = 2-adamantylidene; 2a,b, M = Ru) and Os-bis(dialkylcarbene) complexes [Os(Por)(Ad)2] (3a-c), are synthesized and crystallographically characterized. Detailed investigations into their electronic structures reveal that these complexes are formally low-valent M(ii)-carbene in nature. These complexes display remarkable thermal stability and chemical inertness, which are rationalized by a synergistic effect of strong metal-carbene covalency, hyperconjugation, and a rigid diamondoid carbene skeleton. Various spectroscopic techniques and DFT calculations suggest that the dialkylcarbene Ad ligand is unique compared to other common carbene ligands as it acts as both a potent σ-donor and π-acceptor; its unique electronic and structural features, together with the steric effect of the porphyrin macrocycle, make its Fe porphyrin complex 1a an active and robust catalyst for intermolecular diarylcarbene transfer reactions including cyclopropanation (up to 90% yield) and X-H (X = S, N, O, C) insertion (up to 99% yield) reactions.
Super electron donor-mediated reductive desulfurization reactions
Nozawa-Kumada, Kanako,Ito, Shungo,Noguchi, Koto,Shigeno, Masanori,Kondo, Yoshinori
supporting information, p. 12968 - 12971 (2019/11/05)
The desulfurization of thioacetals and thioethers by a pyridine-derived electron donor is described. This methodology provides efficient access to the reduced products in high yields and does not require the use of transition-metals, elemental alkali-metals, or hydrogen atom donors.
Silica nanoparticles as a reusable catalyst: A straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts under neutral reaction conditions
Banerjee, Subhash,Das, Jayanta,Alvarez, Richard P.,Santra, Swadeshmukul
experimental part, p. 302 - 306 (2010/06/13)
A simple and straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts has been demonstrated using silica nanoparticles (NPs) as a reusable catalyst via the 1,2-addition of thiols to alkenes, alkynes and alkyl/acyl halides, and the 1,4-addition of thiols to conjugated alkenes at room temperature.
Ionic liquid as catalyst and reaction medium: A simple, convenient and green procedure for the synthesis of thioethers, thioesters and dithianes using an inexpensive ionic liquid, [pmIm]Br
Ranu, Brindaban C.,Jana, Ranjan
, p. 1811 - 1818 (2007/10/03)
An easily accessible and inexpensive room temperature ionic liquid, 1-pentyl-3-methylimidazolium bromide, [pmIm]Br efficiently catalyzes the reaction of alkyl halides or acyl halides with thiols without any solvent at room temperature leading to the synthesis of thioethers and thioesters in high yields. This reaction has also been extended for the preparation of dithianes and transthioetherification. The ionic liquid is recovered and recycled for subsequent runs.
A convenient synthesis of some symmetrical and unsymmetrical diarylmethyl sulfur and selenium compounds: X-ray crystal structure of diphenylmethylseleno-2-propene and bis[p-chlorophenyl(phenyl)methyl] diselenide
Bhasin,Singh, Neelam,Kumar, Rajeev,Gupta Deepali,Mehta,Klapoetke, Thomas M.,Crawford
, p. 3327 - 3334 (2007/10/03)
A number of novel and synthetically important symmetrical and unsymmetrical diarylmethyl sulfur and selenium compounds have been synthesized and characterized with the help of elemental analysis and various spectroscopic techniques. The methodology employ
Structure - Activity relationships in 2,2-diphenyl-2-ethylthioacetic acid esters: Unexpected agonistic activity in a series of muscarinic antagonists
Scapecchi,Marucci,Matucci,Angeli,Bellucci,Buccioni,Dei,Gualtieri,Manetti,Romanelli,Teodori
, p. 1165 - 1174 (2007/10/03)
As a continuation of previous research on anticholinergic drugs derived from 2,2-diphenyl-2-ethylthioacetic acid, several 5,5-diphenyl-5-ethylthio-2-pentynamines (2-11) were synthetised and their antimuscarinic activity on M1-4 receptor subtypes was evaluated by functional tests and binding experiments. One of the compounds obtained showed unexpected agonistic activity in functional experiments on M2 receptors. Since the compound carried a phenylpiperazine moiety, other similar compounds (12-17) were prepared and found to be endowed with similar behaviour. These ligands, although possessing the bulky structure characterising muscarinic antagonists, display agonistic activity at M2 subtypes while, as expected, behaving as antagonists on M3 and M4 subtypes. On M1 subtypes, they show agonistic activity which, however, is not blocked by atropine. The peculiar pharmacological profile of these compounds is of interest for studying muscarinic receptor subtypes.
Reactions between Grignard Reagents and Thiocarbonyl Compounds: A Revisitation
Alberti, Angelo,Benaglia, Massimo,Macciantelli, Dante,Marcaccio, Massimo,Olmeda, Antonio,Pedulli, Gian Franco,Roffia, Sergio
, p. 6309 - 6315 (2007/10/03)
The radical anions from thiobenzophenone, thiobenzoyltriphenylsilane, and 3,5-di-tert-butylthio- benzoyltriphenylsilane were detected by EPR spectroscopy when these compounds were reacted with a number of Grignard reagents, RMgBr. The radical adducts resulting from addition of R radicals to the thiones were also detected. The formation of the radical anions indicates unambiguously the occurrence of a SET process which might be the initial stage of these reactions. In the case of tris(trimethylsilyl)ethanethial only the radical adducts were detected. The first reduction potentials of these thiones have also been measured in order to verify the feasibility of the SET process. In agreement with the EPR experiments, the calculated standard free energy changes suggest that electron transfer is possible in the first three cases and disfavored with the thioaldehyde.
Partial Reduction of Dithioacetals with Phosphorus Reagents
Saimoto, Hiroyuki,Kanzaki, Atsuhiro,Miyazaki, Kazumi,Sashiwa, Hitoshi,Shigemasa, Yoshihiro
, p. 2842 - 2844 (2007/10/02)
Acyclic dithioacetals 1 derived from di- and monoaryl ketones were monodesulfurized with diphosphorus tetraiodide or dimethyl phosphonate.A side product 5 from the reaction of 9,9-bis(ethylthio)-9H-fluorene with phosphorus triiodide suggested the intermediacy of an anionic spacies.
New Desulfurizations by Nickel-Containing Complex Reducing Agents
Becker, Sandrine,Fort, Yves,Caubere, Paul
, p. 6194 - 6198 (2007/10/02)
Desulfurizations of saturated aliphatic or aromatic sulfoxides or sulfones are efficiently performed with nickel complex reducing agents (NiCRA's).The complete desulfurization of dithioketals can be effected in high yields with these reagents, while their half-desulfurization is efficiently achieved with 2,2'-bipyridine-modified nickel complex reducing agents (NiCRA-bpy).The desulfurization of vinyl thioethers, sulfoxides, and sulfones have been shown to be chemoselective, leaving the C-C double bond intact.The desulfurization of (E)-PhSO2(CH3)C=CHPh to cis-CH3CH=CHPh with NiCRA in the presence of quinoline is 95percent enantioselective.
Reactions of Triplet Carbenes with Sulfides and Disulfides: Ylide vs. Radical Formation
Alberti, A.,Griller, D.,Nazran, A. S.,Pedulli, G. F.
, p. 3024 - 3028 (2007/10/02)
The reactions between triplet diphenylcarbene and fluorenylidene with a variety of sulfides and disulfides were investigated with use of electron paramagnetic resonance (EPR) spectroscopy, laser flash photolysis, and product studies.Diphenylcarbene reacted with these substrates by a radical-like displacement mechanism.Rate constants were ca. 1E6 M-1 s-1, and the resulting thio-substituted diphenylmethyl radicals were identified by their EPR and optical spectra.By contrast, the analogous reactions of fluorenylidene had rate constants of 1E8-1E9 M-1 s-1 and proceeded by an ylide mechanism.Product studies were consistent with these results but were not sufficient in themselves to reveal these mechanistic differences.
