41578-04-5Relevant academic research and scientific papers
Novel behavior of thiiranium radical cation intermediates. Reactions of dimethyl disulfide with alkenes in the presence of Pd(OAc)2
Takeuchi, Hiroshi,Takatori, Junnichi,Iizuka, Shingo
, p. 916 - 926 (2000)
Reaction of dimethyl disulfide (1) with cyclohexene (2a) in AcOH in the presence of Pd(OAc)2 yields trans-1-acetoxy-2-methylcyclohexane (3a). The equivalent reactions with hex-1-ene (2b) and 2-methylpent-1-ene (2c) or 1-methylcyclohex-1-ene (2d) preferentially give anti-Markovnikov and Markovnikov adducts 4 and 3, respectively, by ace-toxymethylthiolation of the alkene. The Markovnikov regioselectivity 3b/4b for the reaction with 2b (is higher than that for the reaction using AgOAc instead of Pd(OAc)2, which proceeds via a thiiranium ion. Addition of a polar solvent (MeCN or MeNO2) to the reactions with 2b or 2c (using Pd(OAc)2 abnormally decreases the Markovnikov regioselectivity. The total yield of 3 and 4 increases with an increased concentration of AcOH. Compounds 3 and 4 are also formed and the reactions in MeCN or MeNO2 not containing AcOH. A solution of Pd(OAc)2 in 1 exhibits λmax 380 nm (log ε 3.6) assigned to the absorption of a relatively stable sulfonium salt. These indicate that the reactions using Pd(OAc)2 proceed by SN2 ring-opening of a new type of thiiranium radical cations paired with -OAc via the sulfonium salts. The insensitivity of the 3/4 ratios to the reaction time at 25-60°C in the reactions with 2c-d shows the ring-opening to be controlled kinetically, but the increased ratio with reaction time at 116°C in the reaction with 2b suggests that the ring-opening is thermodynamically governed. The reaction product with 2d also undergoes a skeletal rearrangement to a thietanium radical cation to give 1-acetoxymethyl-2-methylthiocyclohexane.
A facile sulfenylchlorination of alkenes with Me2SO/(COCl)2
Lan, Liyuan,Gao, Yang,Ding, Rui,Zhang, Ting,Liu, Yongguo,Sun, Baoguo,Tian, Hongyu
supporting information, p. 539 - 549 (2019/02/01)
The sulfenylchlorination of a series of alkenes is investigated by using the combined reagent of dimethyl sulfoxide and oxalyl chloride. The corresponding β-chloro sulfides were obtained in mediate to good yields. Most of the terminal alkenes give the Mar
Chiral amide directed assembly of a diastereo- and enantiopure supramolecular host and its application to enantioselective catalysis of neutral substrates
Zhao, Chen,Sun, Qing-Fu,Hart-Cooper, William M.,Dipasquale, Antonio G.,Toste, F. Dean,Bergman, Robert G.,Raymond, Kenneth N.
supporting information, p. 18802 - 18805 (2014/01/06)
The synthesis of a novel supramolecular tetrahedral assembly of K 12Ga4L6 stoichiometry is reported. The newly designed chiral ligand exhibits high diastereoselective control during cluster formation, leading exclusively t
Conformational analysis of 1-Y, 2-Z-cyclohexanes ( Y = OH, OMe, F, Cl, Br and I; Z= SMe, SOMe and SO2Me): Study of the Z/Y gauche interactions
Carreno,Carretero,Garcia Ruano,Rodriguez
, p. 5649 - 5664 (2007/10/02)
The conformational study of the title compounds is reported. The configurational assignment of the epimeric sulfoxides was based on the relationship between the stereochemistry of the sulfinyl group and the chemical shifts of the neighboring nuclei. The v
Studies on the Stereoselectivity of Hydride Reductions on 2-(Methylthio)- and 2-(Methylsulfonyl)cyclohexanones
Carreno, M. Carmen,Dominguez, Enrique,Garcia-Ruano, Jose L.,Rubio, Almudena
, p. 3619 - 3625 (2007/10/02)
The results obtained in the reductions of 2-X-cyclohexanones and cis- and trans-4-tert-butyl-2-X-cyclohexanones (X=SMe, SO2Me) with different hydrides are reported.When the sulfur functions adopt the axial disposition, the cyclohexanol resulting from the
