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Molecules 2000, 5(7), 916-926; doi:10.3390/50700916
Article

Novel Behavior of Thiiranium Radical Cation Intermediates. Reactions of Dimethyl Disulfide with Alkenes in the Presence of Pd(OAc)2

* ,  and
Department of Chemical Science and Engineering, Faculty of Engineering, Kobe University, Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan
* Author to whom correspondence should be addressed.
Received: 8 March 2000 / Revised: 7 June 2000 / Accepted: 20 June 2000 / Published: 7 July 2000
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Abstract

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 acetoxymethylthiolation 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 ringopening 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.
Keywords: Dimethyl disulfide; Palladium (II) acetate; Acetoxymethylthiolation; Thiiranium radical cation; Regioselectivity for SN2 ring-opening; Solvent effects; Thietanium radical cation; Skeletal rearrangement Dimethyl disulfide; Palladium (II) acetate; Acetoxymethylthiolation; Thiiranium radical cation; Regioselectivity for SN2 ring-opening; Solvent effects; Thietanium radical cation; Skeletal rearrangement
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).
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Takeuchi, H.; Takatori, J.; Iizuka, S. Novel Behavior of Thiiranium Radical Cation Intermediates. Reactions of Dimethyl Disulfide with Alkenes in the Presence of Pd(OAc)2. Molecules 2000, 5, 916-926.

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