- Photocatalytic Deoxygenation of Sulfoxides Using Visible Light: Mechanistic Investigations and Synthetic Applications
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The photocatalytic deoxygenation of sulfoxides to generate sulfides facilitated by either Ir[(dF(CF3)ppy)2(dtbbpy)]PF6 or fac-Ir(ppy)3 is reported. Mechanistic studies indicate that a radical chain mechanism operates, which proceeds via a phosphoranyl radical generated from a radical/polar crossover process. Initiation of the radical chain was found to proceed via two opposing photocatalytic quenching mechanisms, offering complementary reactivity. The mild nature of the radical deoxygenation process enables the reduction of a wide range of functionalized sulfoxides, including those containing acid-sensitive groups, in typically high isolated yields.
- Clarke, Aimee K.,Parkin, Alison,Rossi-Ashton, James A.,Taylor, Richard J. K.,Unsworth, William P.
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p. 5814 - 5820
(2020/07/21)
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- Synthesis of aryl cyclopropyl sulfides through copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid
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The copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid is reported. The procedure operates under simple conditions to afford the corresponding aryl cyclopropyl sulfides in moderate to excellent yields. The reaction tolerates substitution in ortho-, meta- and para-substitution as well as electron-donating and electron-withdrawing groups. The S-cyclopropylation of a thiophenol was also accomplished using potassium cyclopropyl trifluoroborate.
- Benoit, Emeline,Fnaiche, Ahmed,Gagnon, Alexandre
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p. 1162 - 1171
(2019/06/08)
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- First use of an organobismuth reagent in C(sp3)–S bond formation: Access to aryl cyclopropyl sulfides via copper-catalyzed S–Cyclopropylation of thiophenols using tricyclopropylbismuth
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The direct S-cyclopropylation of thiophenols using tricyclopropylbismuth is reported. The reaction is catalyzed by copper(II) acetate and operates under mild conditions to afford the corresponding aryl cyclopropyl sulfides in moderate to good yields. This reaction represents the first use of an organobismuth reagent in C(sp3)–S bond formation.
- Benoit, Emeline,Bueno, Bianca,Choinière, Catherine,Gagnon, Alexandre
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supporting information
p. 72 - 77
(2019/05/15)
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- Synthesis method of thioether compounds
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The invention discloses a synthesis method of thioether compounds. The method comprises steps as follows: phosphorus trichloride and a solvent with uniformly distributed sulfoxide compounds are mixeduniformly, after mixing, the mixture is subjected to a reaction at the temperature of 20-25 DEG C for 0.5-6 h, and the thioether compounds are obtained, wherein the solvent is acetonitrile. Compared with the prior art, the synthesis method has the advantages that raw materials are cheap and easy to obtain, a reducer is cheap and easy to obtain and store, and a series of thioether compounds can beobtained.
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Paragraph 0077-0081
(2019/08/02)
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- Deoxygenation of sulphoxides to sulphides with trichlorophosphane
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An efficient route to deoxygenation of sulphoxides to sulphides with PCl3 under mild reaction condition was developed. PCl3 was used as a reducing agent for the first time to convert sulphoxides to sulphides. The mild conditions, use of cheap and readily available reagent, and broad substrate scope render it a useful strategy for preparing sulphides.
- Zhao, Xia,Zheng, Xiancai,Yang, Bo,Sheng, Jianqiao,Lu, Kui
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p. 1200 - 1204
(2018/02/21)
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- Discovery of liver-directed glucokinase activator having anti-hyperglycemic effect without hypoglycemia
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Glucokinase activators (GKAs) are among the emerging drug candidates for the treatment of type 2 diabetes (T2D). Despite effective blood glucose lowering in clinical trials, many pan-GKAs “acting both in pancreas and liver” have been discontinued from cli
- Deshpande, Anil M.,Bhuniya, Debnath,De, Siddhartha,Dave, Bhavesh,Vyavahare, Vinod P.,Kurhade, Santosh H.,Kandalkar, Sachin R.,Naik, Keshav P.,Kobal, Balasaheb S.,Kaduskar, Rahul D.,Basu, Sujay,Jain, Vaibhav,Patil, Pratima,Chaturvedi Joshi, Sandhya,Bhat, Ganesh,Raje, Amol A.,Reddy, Satyanarayana,Gundu, Jayasagar,Madgula, Vamsi,Tambe, Suhas,Shitole, Prasad,Umrani, Dhananjay,Chugh, Anita,Palle, Venkata P.,Mookhtiar, Kasim A.
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p. 268 - 286
(2017/04/13)
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- A practical and chemoselective Mo-catalysed sulfoxide reduction protocol using a 3-mercaptopropyl-functionalized silica gel (MPS)
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A convenient sulfoxide deoxygenation procedure using a mercaptopropyl-functionalized silica gel as the reducing agent is described. This new protocol based on a heterogeneous reagent displays broad scope and tolerance to reducible functional groups and, from an experimental point of view, enhances previous methods by simplifying the isolation of the sulfide to a simple filtration.
- García, Nuria,Fernández-Rodríguez, Manuel A.,García-García, Patricia,Pedrosa, María R.,Arnáiz, Francisco J.,Sanz, Roberto
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p. 27083 - 27086
(2016/03/25)
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- An unprecedented use for glycerol: Chemoselective reducing agent for sulfoxides
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A new application for glycerol that expands its possibilities beyond a green solvent and a precursor of value-added products has been demonstrated. Simple, easily available, and environmentally friendly dioxomolybdenum(vi) complexes are highly efficient catalysts for the chemoselective sulfoxide deoxygenation with this biomass-derived chemical feedstock. Both refined glycerol and crude glycerin can be used, thus expanding the potential application of this reaction. Subsequent transformation of glycerol during this reductive process has also been investigated.
- Garcia, Nuria,Garcia-Garcia, Patricia,Fernandez-Rodriguez, Manuel A.,Garcia, Daniel,Pedrosa, Maria R.,Arnaiz, Francisco J.,Sanz, Roberto
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supporting information
p. 999 - 1005
(2013/07/25)
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- Sulfoxide-to-sulfilimine conversions: Use of modified Burgess-type reagents
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Sulfoxides can directly be converted into N-cyanosulfilimines using a new Burgess-type reagent. By applying this strategy with a related reagent variant, synthetically valuable NH-sulfoximines have been prepared from sulfoxides via N-protected sulfilimines. The practical three-step reaction sequence is generally high yielding and applicable to a wide range of substrates. The sulfoxide-to-sulfilimine conversion can also be performed under solvent-reduced conditions in a ball mill. Copyright
- Hendriks, Christine M. M.,Lamers, Philip,Engel, Julien,Bolm, Carsten
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supporting information
p. 3363 - 3368
(2013/12/04)
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- The effect of ring size on reactivity: The diagnostic value of 'rate profiles'
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The rates of cycloalkyl phenyl sulfide formation of a series of homologous bromocycloalkanes upon treatment with sodium benzenethiolate have been determined to ascertain the effect of ring size on reactivity. The 'rate profile', i.e., reaction rate vs. ring size, for these nucleophilic substitutions (SN2) was determined. A linear free-energy relationship could be derived from computed hydride affinities of cycloalkanes and rates of typical SN1 reactions, whereas rates of SN2 reactions exhibited a strong discrepancy from the seven- up to the twelve-membered rings. This discrepancy was rationalized by a careful examination of the geometry of the intermediates and transition states involved in these reactions.
- Masson, Eric,Leroux, Frederic
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p. 1375 - 1386
(2007/10/03)
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- Cyclopropyl-containing photoacid generators for chemically amplified resists
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Several cyclopropyl-containing photoacid generators (PAGs) were synthesized in order to reduce absorbance at 193 nm and induce the photobleaching effect. From the GC-mass experiment, cleavage of S-C(cyclopropyl) which is more preferential than that of S-C
- Kim, Jin-Baek,Jang, Ji-Hyun,Kim, Hyun-Woo,Woo, Sang-Gyun
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p. 554 - 555
(2007/10/03)
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- The phenylthiocyclopropylsilyl group: A useful latent hydroxy group
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The α-dimethyl(1-phenylthio)cyclopropylsilyl group was used as a new masked hydroxy group. Three procedures have been devised to allow the oxidation of this silicon group in the presence of various functionalities. The desired alcohols are obtained in high yields with retention of configuration at the carbon centre. (C) 2000 Elsevier Science Ltd.
- Angelaud, Rémy,Landais, Yannick
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p. 2025 - 2036
(2007/10/03)
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- 1-METHOXY-1-(PHENYLTHIO)CYCLOPROPANES FROM OLEFINS VIA THE PUMMERER REARRANGEMENT
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The Pummerer rearrangements of cyclopropyl(methoxy)phenylsulfonium salts proceed via sulfur-stabilized carbocations to yield the title compounds.The sulfonium salts were prepared in high yields from olefins via carbene addition, oxidation, and methylation
- Bhupathy, M.,Cohen, Theodore
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p. 4797 - 4800
(2007/10/02)
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- SRN1 Reactions of Halocyclopropanes with Benzenethiolate Ion
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Ultraviolet irradiation of gem-dibromocyclopropanes 1 with benzenethiolate ion in liquid ammonia or in Me2SO solutions gave dithioacetals 2 and, in some cases, cyclopropyl phenyl sulfides 3.The reactions did not proceed in the dark and they were inhibited by m-dinitrobenzene, di-tert-butyl nitroxide, and oxygen.The bromocyclopropane 6a underwent a similar, but slower, reaction.Treatment of the bromochlorocyclopropane 7b led to replacement of only the bromine, while the dichlorocyclopropane 9b was inert under the reaction conditions.The results appear consistent with a radical chain mechanism.
- Meijs, Gordon F.
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p. 606 - 611
(2007/10/02)
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- THE REACTION OF β-STANNYL CARBONYL COMPOUNDS WITH LEWIS ACIDS
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β-Stannyl carbonyl compounds, when treated with Lewis acids, afforded cyclopropane derivatives or ketones, and the reaction was applied to the synthesis of β,γ-enones from α,β-enones.
- Sato, Tadashi,Watanabe, Masami,Murayama, Eigoro
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p. 1621 - 1624
(2007/10/02)
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- NEW SYNTHETIC REACTIONS CONTRIBUTED BY SULPHUR
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Eighteen kinds of new convenient synthetic reactions respectively contributed by divalent sulfur (7), sulfoxide (7) and sulfone (4) are shown.
- Kaji, Aritsune
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p. 211 - 222
(2007/10/02)
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- The chemistry of small ring compounds. Part 46. Reduction of 1-halocyclopropyl sulfides by thiolates
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The reaction of 1-halocyclopropyl sulfides with sodium alkanethiolates in protic or aprotic solvents leads to high yields of cyclopropyl sulfides, in which halogen has been replaced by hydrogen.The complementary oxidized product is, in most cases, the thioketone or thioaldehyde derived from the alkanethiolate.The reduction is unaffected by radical scavengers or by one-electron donors.Reaction kinetics indicate that the reduction proceeds via the 1-(alkylthio)cyclopropyl cation.A mechanism is discussed (Scheme 9) in which this ambident cation is attacked by thiolate on sulfur.In the intermediary sulfonium ylid an intramolecular hydrogen shift leads to the observed products.
- Jorritsma, R.,Steinberg, H.,Boer, Th. J. de
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p. 288 - 298
(2007/10/02)
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- A New and Convenient Synthetic Method for Cyclopropyl Phenyl Sulfides
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The reactions of a variety of 1,3-bis(phenylthio)propanes with butyllithium have been shown to produce cyclopropyl phenyl sulfides in good to high yields.A new and convenient in situ preparation of 1-lithiocyclopropyl phenyl sulfide can be readily carried out by treating 1,3-bis(phenylthio)propane with 2 equiv. of butyllithium at 0 degC in THF.The reaction with electrophiles proceeds in good yield.O-Aryl and O-alkyl S-cyclopropyl dithiocarbonates also can be prepared in good yields. 1,2-Bis(phenylthio)ethane was converted to phenyl vinyl sulfide on treatment with butyllithium, while 1,4-bis(phenylthio)butane was recovered unchanged by a similar treatment.
- Tanaka, Kazuhiko,Uneme, Hideki,Matsui, Shuichi,Kaji, Aritsune
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p. 2965 - 2972
(2007/10/02)
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- A SIMPLE, HIGHLY VERSATILE SYNTHESIS OF CYCLOPROPYL PHENYL SULFIDES
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1,3-Bis(phenylthio)propane reacted readily with 2-2.2 equiv. of n-butyllithium in THF at 0 degC to afford 1-lithiocyclopropyl phenyl sulfide.Treatment of the substituted 1,3-bis(phenylthio)propanes with 1.1 equiv. of n-butyllithium afforded the correspond
- Tanaka, Kazuhiko,Uneme, Hideki,Matsui, Syuichi,Tanikaga, Rikuhei,Kaji, Aritsune
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p. 287 - 288
(2007/10/02)
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