139-66-2Relevant articles and documents
Exploring Regioselective Bond Cleavage and Cross-Coupling Reactions using a Low-Valent Nickel Complex
Desnoyer, Addison N.,Friese, Florian W.,Chiu, Weiling,Drover, Marcus W.,Patrick, Brian O.,Love, Jennifer A.
, p. 4070 - 4077 (2016)
Recently, esters have received much attention as transmetalation partners for cross-coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}2(μ-η2:η2-C6H6)] (dtbpe=1,2-bis(di-tert-butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η2-carbonyl complexes. In contrast, acetylthioesters underwent rapid Cacyl-S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross-coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an η2-carbonyl complex, phenyl esters were found to predominantly undergo Caryl-O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2-naphthyl acetate was also found to undergo clean Caryl-O bond cleavage, and although stoichiometric cross-coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive. The reactivity of a low-valent nickel complex with esters and thioesters is reported. Trifluoromethylthioesters were found to form η2-carbonyl complexes, while acetylthioesters were found to undergo further Cacyl-S oxidative addition and decarbonylation to generate methylnickel complexes. In contrast, the same nickel precursor was found to induce Caryl-O bond cleavage in aryl esters to generate arylnickel acetate complexes (see scheme).
Synthesis, Electronic Structure, and Reactivities of Two-Sulfur-Stabilized Carbones Exhibiting Four-Electron Donor Ability
Morosaki, Tomohito,Iijima, Ryo,Suzuki, Tsubasa,Wang, Wei-Wei,Nagase, Shigeru,Fujii, Takayoshi
, p. 8694 - 8702 (2017)
Bis(sulfane)carbon(0) (BSC; Ph2S→C←SPh2 (1)) is successfully synthesized by deprotonation of the corresponding protonated salt 1?HTfO. The diprotonated salt 1?(HTfO)2 as the starting material can be also easily accessed by
Reaction of benzyne with formamides and acetylimidazole
Okuma, Kentaro,Nojima, Akiko,Nakamura, Yuki,Matsunaga, Nahoko,Nagahora, Noriyoshi,Shioji, Kosei
, p. 328 - 332 (2011)
The reaction of DMF with o-trimethylsilylphenyl triflate in the presence of CsF afforded dimethyldiphenylammonium triflate, xanthene, and xanthone in 62%, 16%, and 24% yields, respectively. On the other hand, the reaction of dimethylthioformamide with triflate and CsF resulted in diphenyl sulfide, xanthene, and xanthone in 62%, 10%, and 12% yields, respectively. The reaction of acetylimidazole with benzyne gave 9-N,N-diphenylaminoanthracene in 85% yield.
A stable amine functionalized montmorillonite supported Cu, Ni catalyst showing synergistic and co-operative effectiveness towards C-S coupling reactions
Varadwaj, G. Bishwa Bidita,Rana, Surjyakanta,Parida
, p. 7570 - 7578 (2013)
The objective of this work is to prepare a cheap and highly stable heterogeneous catalyst. This was done by a simple two step approach. The first step involved the preparation of an organic-inorganic hybrid material by covalent grafting of amines on K10 m
Cyclopropyl-containing photoacid generators for chemically amplified resists
Kim, Jin-Baek,Jang, Ji-Hyun,Kim, Hyun-Woo,Woo, Sang-Gyun
, p. 554 - 555 (2003)
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
High activity and stability in the cross-coupling of aryl halides with disulfides over Cu-doped hierarchically porous zeolite ZSM-5
Fu, Wenqian,Liu, Taotao,Fang, Zhongxue,Ma, Yuli,Zheng, Xiang,Wang, Wenchang,Ni, Xiaojun,Hu, Maolin,Tang, Tiandi
, p. 5890 - 5893 (2015)
A Cu-doped zeolite ZSM-5 (Cu-ZSM-5-M) with a micro-meso-macroporous structure was directly synthesized, and it exhibits excellent catalytic activity and good recyclability in the cross-coupling of aryl halides with diphenyl disulfides. This feature should be attributed to the structural characteristics of meso-macropores and homogeneous dispersion of active Cuδ+ (δ 2) species in Cu-ZSM-5-M.
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Still,I.W.J.,Turnbull,K.
, p. 540 - 541 (1978)
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Hartman,Smith,Dickey
, p. 1317 (1932)
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Toussaint
, p. 319,357, 358 (1945)
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Dougherty,Hammond
, p. 117 (1935)
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Cu-Catalyzed o-Amino Benzofuranthioether Formation from N-Tosylhydrazone-Bearing Thiocarbamates and Arylative Electrophiles
Li, Xue,Mai, Shaoyu,Li, Xin,Xu, Jian,Xu, Hetao,Song, Qiuling
, p. 7874 - 7878 (2020)
An important framework of o-amino benzofuranthioethers was constructed by Cu-catalyzed arylative cyclization of N-tosylhydrazone-bearing thiocarbamates with silylaryl triflates or ArI. This transformation provides a novel strategy for the synthesis of valuable arylative o-amino benzofuranthioethers in moderate yields which could not be obtained from known methods. The reaction features smart design, efficient construction, and mild reaction conditions.
Polystyryldiphenylphosphine as a Deoxygenation Reagent for Sulfoxides
Amos, Richard A.
, p. 1311 - 1313 (1985)
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Harrington et al.
, p. 1079 (1972)
PHASE-TRANSFER CATALYSIS IN THE NICKEL- AND PALLADIUM-CATALYZED FORMATION OF ARYL AND ALKENYL SULFIDES
Foa, M.,Santi, R.,Garavaglia, F.
, p. C29 - C32 (1981)
Aryl and alkenyl sulfides can be conveniently prepared from the corresponding halides and alkaline thiolates under phase transfer conditions in the presence of ?-Aryl-Ni2Cl or ?-Aryl-Pd2Br.
Microwave-assisted Ullmann C-S bond formation: Synthesis of the P38α MAPK clinical candidate VX-745
Bagley, Mark C.,Davis, Terence,Dix, Matthew C.,Fusillo, Vincenzo,Pigeaux, Morgane,Rokicki, Michal J.,Kipling, David
, p. 8336 - 8342 (2009)
(Chemical Equation Presented) Microwave irradiation promotes the rapid and efficient reaction of a thiophenol and aryl or heteroaryl halide using a copper or palladium catalyst and a range of ligands, depending upon substrate. Of particular utility is the use of copper(I) iodide (5 mol %) and trans-cyclohexane-1,2-diol as ligand under basic conditions and microwave irradiation to give the corresponding sulfide in high yield. This method for C-S bond formation is applied in the four-step synthesis of the clinical candidate VX-745 in 38% overall yield. The inhibitory activity of VX-745 against p38α MAPK is confirmed in Werner syndrome dermal fibroblasts at 1.0 μM concentration by immunoblot assay. 2009 American Chemical Society.
First Preparation and X-ray Crystallographic Structure Determination of S,S,S-Triphenylthiazyne
Yoshimura, Toshiaki,Hamada, Kohki,Imado, Masahiro,Hamata, Kouki,Tomoda, Kazumi,Fujii, Takayoshi,Morita, Hiroyuki,Shimasaki, Choichiro,Ono, Shin,Tsukurimichi, Eiichi,Furukawa, Naomichi,Kimura, Takeshi
, p. 3802 - 3803 (1997)
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Molybdenum oxo-peroxo complex: A very fast catalyst for oxidation and reduction of sulfur-based compounds
Bagherzadeh, Mojtaba,Haghdoost, Mohammad Mehdi,Amini, Mojtaba,Derakhshandeh, Parviz Gohari
, p. 14 - 19 (2012)
We have evaluated the catalytic activity of a molybdenum(VI) oxo-peroxo complex through the oxidation and reduction of sulfur-based compounds. Arylalkyl, diaryl and dialkyl sulfides are selectively oxidized to corresponding sulfoxides, with tert-butyl hydroperoxide (TBHP), in the presence of MoO(O 2)(phox)2 complex as catalyst. This molybdenum complex was also found to be an efficient catalyst for the deoxygenation of sulfoxides to sulfides with PPh3 in excellent yields and chemoselectivity.
In situ synthesis of sub-nanometer metal particles on hierarchically porous metal-organic frameworks via interfacial control for highly efficient catalysis
Zhang, Pei,Chen, Chunjun,Kang, Xinchen,Zhang, Lujun,Wu, Congyi,Zhang, Jianling,Han, Buxing
, p. 1339 - 1343 (2018)
In this work, we developed a strategy to in situ synthesize sub-nanometer metal particle/hierarchically mesoporous metal-organic framework (MOF) composites in emulsion. In this route, water droplets in the emulsion acted as both a solvent of the metal pre
PHOSPHA-S-TRIAZINES. X. THIOPHENYL-SUBSTITUTED PHOSPHA-S-TRIAZINES
Paciorek, K. J. L.,Harris, D. H.,Nakahara, J. H.,Smythe, M. E.,Kratzer, R. H.
, p. 399 - 416 (1985)
A series of thiophenyl-substituted mono- and diphospha-s-triazines was prepared.These materials exhibited physical characteristics similar to those of the corresponding phenyl analogues, but the mass spectral breckdown patterns were dominated by the loss of the thiophenyl group and differed significantly from that of the other phospha-s-triazines investigated to date.The thiophenyl-phospha-s-triazines exhibited anticorrosive and antioxidative action when used as additives in perfluoroalkylether fluids.At elevated temperatures, 316 deg C, these materials were less effective than the phenyl analogues.The monophospha-members of the series were thermally and oxidatively less stable the corresponding diphospha-s-triazines: 67 versus 96percent starting material recovery after exposure to air at 235 deg C for 24 hr.Both the mono- and diphospha-s-triazines were completely degraded in 24 hr at 316 deg C in nitrogen.
Cu attached functionalized mesoporous MCM-41: a novel heterogeneous nanocatalyst for eco-friendly one-step thioether formation reaction and synthesis of 5-substituted 1H-tetrazoles
Molaei, Somayeh,Ghadermazi, Mohammad
, p. 4557 - 4581 (2021)
In the current study, a mesoporous copper-attached functionalized MCM-41 with the DL-Pyroglutamic acid framework has been produced through a post-synthetic method. The MCM-41 functionalization technique has been used to synthesize this novel heterogeneous catalyst. The material has been identified fully using XRD, FT-IR, BET, EDX, elemental mapping, SEM, and TGA. This catalyst displays high catalytic performance in the one-step thioether formation (C–S) reaction and synthesis of 5-substituted 1H-tetrazoles. The main aspects of this economical copper-catalyzed procedure are green synthesis, slighter experimental conditions, and less reaction time with no additives. Further benefits comprise experimental comfort of handling, secure replacement to dangerous, damaging, and poisoning regular Lewis’s acid catalysts, and reusability with constant catalytic performance. Graphic abstract: [Figure not available: see fulltext.]
Domino Processes of Arynes Reacting with Three Classes of Nucleophiles for Organic Syntheses
Hwu, Jih Ru,Panja, Avijit,Gupta, Nitesh K.,Hu, Yu-Chen,Tan, Kui-Thong,Lin, Chun-Cheng,Hwang, Kuo-Chu,Hsu, Ming-Hua,Huang, Wen-Chieh,Tsay, Shwu-Chen
, p. 683 - 693 (2021)
Synthetic application of arynes is broadened by their reactions with neutral N-, S-, and O-containing nucleophiles to produce three types of compounds. Accordingly, 1,2-dihydroquinolines are synthesized from Schiff bases, alkynes, and arynes through a Diels-Alder reaction. Epoxides are prepared from thioethers and arynes along with aldehydes or ketones through a Johnson-Corey-Chaykovsky reaction. Phenolic ethers are produced from allyl ethers and arynes through a Claisen-type rearrangement. These target molecules, including natural products γ-asarone, asaricin, and a cholesteryl phenolic ether, are formed through reactions initiated by arynes. These new reactions share a prevailing feature of domino processes, which are carried out in a single flask and afford the desired products in good to high yields.
The syntheses of sulfides by deoxygenation of sulfoxides using Woollins' reagent
Hua, Guoxiong,Woollins, J. Derek
, p. 3677 - 3679 (2007)
Woollins' reagent (WR) acts as a deoxygenation reagent for a wide range of sulfoxides affording the corresponding sulfides in good to excellent yields (up to 99% isolated yield) under mild conditions.
TFAA/DMSO-Promoted Fluorination of P(O)?H and P(O)?OH Compounds: Compatible Access to Fluorophosphonates and Phosphonofluoridates
Li, Qi-Wei,Zhang, Xin-Yue,Lu, Lu,Wu, Zi-Qian,Li, Ji,Li, Gui-Zhi,Sun, Kai,Yang, Shang-Dong,Yang, Bin
supporting information, p. 938 - 946 (2022/02/07)
A TFAA/DMSO/NaF-based system for the efficient fluorination of P(O)?H and P(O)?OH compounds has been developed. Without adding highly toxic and expensive fluorination reagents, this novel transformation provides direct and compatible access to a variety o
N-bromosuccinimide/HCl mediated reduction of sulfoxides to sulfides
Wang, Jianqiang,Shi, Fangmin,Dai, Dongyan,Xiong, Liping,Yang, Yongpo
supporting information, p. 439 - 443 (2021/02/03)
An efficient reduction of sulfoxides to sulfides mediated by N-bromosuccinimide (NBS)/HCl system has been developed. This protocol shows good functional group compatibility as well as broad substrates scope with operational simplicity.
