5633-34-1Relevant articles and documents
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Ratts,K.W.,Yao,A.N.
, p. 1185 - 1188 (1966)
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Synthesis of functionalized thietanes via electrophilic carbenoid-induced ring expansion of thiiranes with sulfonium acylmethylides as carbene precursors
Dong, Jun,Du, Hongguang,Xu, Jiaxi
, p. 10724 - 10739 (2019/09/30)
Various functionalized thietanes were prepared from thiiranes via an electrophilic ring expansion with rhodium carbenoids as electrophiles generated from safe and readily accessible dimethylsulfonium acylmethylides. The reaction appears to proceed through electrophilic metallocarbenoid-induced activation of thiiranes, nucleophilic ring-opening of the activated thiiranes with dimethyl sulfide as a transient nucleophile, and nucleophilically intramolecular cyclization. The Umpolung from the nucleophilic ylides to the electrophilic carbenoids plays an important role in both the activation and ring opening of thiiranes and subsequent cyclization. The current method provides a new strategy for the efficient preparation of functionalized thietanes from readily available thiiranes.
New Pd(II) complexes of sulfur ylides; Synthesis, X-ray characterization, a theoretical study and catalytic activity toward the Mizoroki-Heck reaction
Sabounchei,Ahmadianpoor,Yousefi,Hashemi,Bayat,Sedghi,Akhlaghi Bagherjeri,Gable
, p. 28308 - 28315 (2016/04/09)
The reaction of sulfur ylides (L) SMe2C(H)C(O)R (R = 4-nitrophenyl, phenyl, and 3-nitrophenyl) with the dichloro(1,5-cyclooctadiene)palladium(II) complex, [PdCl2(cod)], in a 2:1 ratio gives the new Pd(II) complexes of type cis- and trans-[PdCl2(SMe2C(H)C(O)R)2] (R = phenyl (1), 3-nitrophenyl (2), and 4-nitrophenyl (3)). Characterization of the obtained complexes was performed by elemental analysis, IR, 1H, 13C NMR and mass spectroscopies. Also, the structure of complex trans-[PdCl2(SMe2C(H)C(O)C6H4-p-NO2)2] (3) was characterized by single crystal X-ray analysis. The X-ray crystallography results reveal that the structure of complex 3 contains two Cα-coordinated sulfur ylide ligands in trans geometry. These air/moisture stable complexes were also employed as efficient catalysts for the Mizoroki-Heck cross-coupling reaction of several aryl halides with olefins. The coupled products of these reactions were obtained in good to excellent yields and purity, short reaction times and low catalyst loading. Also a theoretical study on the structure of the complexes 1-3 have been investigated at the BP86/def2-SVP level of theory. The bonding situation between the [PdCl2] and L2 fragments [(Ylide)2] in the [L2PdCL2] complexes, were carried out by NBO and energy-decomposition analysis (EDA), as well as their natural orbitals for chemical valence variation (EDA-NOCV). The results confirmed that the contribution of the electrostatic interactions in the Pd-C bond in the complexes is about 50%.