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
The reaction of 4,5-dichloro-1,2,3-dithiazolium chloride with DMSO: an improved synthesis of 4-chloro-1,2,3-dithiazol-5H-one
Kalogirou, Andreas S.,Koutentis, Panayiotis A.
, p. 6855 - 6858 (2009)
4,5-Dichloro-1,2,3-dithiazolium chloride 2 (Appel salt) reacts with either DMSO, diphenylsulfoxide 11 or methylphenylsulfoxide 12 to give 4-chloro-5H-1,2,3-dithiazol-5-one 1 in excellent yields. The use of catalytic amounts of DMSO (1 mol %) in MeCN in th
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.
Concerted aryl-sulfur reductive elimination from PNP pincer-supported Co(iii) and subsequent Co(i)/Co(iii) comproportionation
Foley, Bryan J.,Palit, Chandra Mouli,Bhuvanesh, Nattamai,Zhou, Jia,Ozerov, Oleg V.
, p. 6075 - 6084 (2020)
This report discloses a combined experimental and computational study aimed at understanding C-S reductive elimination from Co(iii) supported by a diarylamido/bis(phosphine) PNP pincer ligand. Divalent (PNP)Co-aryl complexes could be easily oxidized to five-coordinate Co(iii) derivatives, and anion metathesis provided five-coordinate (PNP)Co(Ar)(SAr′) complexes of Co(iii). In contrast to their previously described (POCOP)Co(Ar)(SAr′) analogs, but similarly to the (PNP)Rh(Ar)(SAr′) and (POCOP)Rh(Ar)(SAr′) analogs, (PNP)Co(Ar)(SAr′) undergo C-S reductive elimination with the formation of the desired diarylsulfide product ArSAr′. DFT studies and experimental observations are consistent with a concerted process. However, in contrast to the Rh analogs, the immediate product of such reductive elimination, the unobserved Co(i) complex (PNP)Co, un-dergoes rapid comproportionation with the (PNP)Co(Ar)(SAr′) starting material to give Co(ii) compounds (PNP)Co-Ar and (PNP)Co-SAr′.
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
A novel synthesis of diaryl sulfides
Wang,Hay
, p. 5685 - 5686 (1990)
Reaction of diphenyl disulfide and aryl iodides or diiodides at high temperature affords phenyl aryl sulfides or bis(phenylthio)arenes in good yields. Thermolysis of dialkyl disulfide with aryl iodides yields only diaryl sulfides.
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.
Room-temperature carbon-sulfur bond formation from Ni(II) σ-aryl complex via cleavage of the S-S bond of disulfide moieties
Okamoto, Ken,Housekeeper, Jeremy B.,Luscombe, Christine K.
, p. 639 - 643 (2013)
The formation of ArSY (Y: C(= S)NMe2, Ph, P(= O)(OEt) 2) by reductive elimination from σ-aryl complexes (M(PPh 3)2PhBr, M = Ni, Pd), associated with disulfides (YS-SY, Y: C(=S)NMe2 (1), Ph (2), P(=O)(OEt)2 (3)), at ambient temperature, has been investigated. Various mechanistic features of disulfide bond (S-S) cleavage have been elucidated using disulfide 1 by 31P NMR spectroscopy and matrix-assisted laser desorption/ionization-time of flight mass spectrometric investigations. Based upon the results of nucleophilic cleavage of the S-S bond by PPh3, studies of the reductive elimination process show that when M(PPh3)2PhBr is mixed with disulfide 1, competitive reactions occur between the PPh3 ligand, disulfide 1 and a trace amount of water, leading to low C-S coupling yields; an oxidation reaction of PPh3 with disulfide and water occur prior to C-S cross-coupling, and phosphonium ion intermediates are likely involved. However, when the disulfide 1 is pretreated with PPh3, the Ni(II) σ-aryl complex affords the C-S coupling product nearly quantitatively at room temperature. The pretreatment method is also effective for the coupling reaction of disulfide 2 and Ni(II) σ-aryl complex. The difference between Ni(II) and Pd(II) σ-aryl complexes on C-S bond formation by reductive elimination can be explained by the affinity of metal for the thiolate ligands derived from the cleaved disulfide. Copyright 2013 John Wiley & Sons, Ltd. The formation of ArSY (Y: C(= S)NMe2, Ph, P(= O)(OEt)2) by reductive elimination from σ-aryl complexes (M(PPh3)2PhBr, M = Ni, Pd) at ambient temperature, has been investigated, a result that shows an effective C-S cross-coupling reaction. Copyright
