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Dehydration Reaction of Hydroxyl Substituted Alkenes and Alkynes on the Ru2S2 Complex

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journal contribution
posted on 11.10.2002, 00:00 by Kazuko Matsumoto, Yoshihiro Moriya, Hiroyasu Sugiyama, Md. Munkir Hossain, Yong-Shou Lin
A variety of inter- and intramolecular dehydration was found in the reactions of [{Ru(P(OCH3)3)2(CH3CN)3}2(μ-S2)](CF3SO3)4 (1) with hydroxyl substituted alkenes and alkynes. Treatment of 1 with allyl alcohol gave a C3S2 five-membered ring complex, [{Ru(P(OCH3)3)2(CH3CN)3}2{μ-SCH2CH2CH(OCH2CHCH2)S}](CF3SO3)4 (2), via C−S bond formation after C−H bond activation and intermolecular dehydration. On the other hand, intramolecular dehydration was observed in the reaction of 1 with 3-buten-1-ol giving a C4S2 six-membered ring complex, [{Ru(P(OCH3)3)2(CH3CN)3}2 {μ-SCH2CHCHCH2S}](CF3SO3)4 (3). Complex 1 reacts with 2-propyn-1-ol or 2-butyn-1-ol to give homocoupling products, [{Ru(P(OCH3)3)2(CH3CN)3}2{μ-SCRCHCH(OCH2C⋮CR)S}](CF3SO3)4 (4:  R = H, 5:  R = CH3), via intermolecular dehydration. In the reaction with 2-propyn-1-ol, the intermediate complex having a hydroxyl group, [{Ru(P(OCH3)3)2(CH3CN)3}2{μ-SCHCHCH(OH)S}](CF3SO3)4 (6), was isolated, which further reacted with 2-propyn-1-ol and 2-butyn-1-ol to give 4 and a cross-coupling product, [{Ru(P(OCH3)3)2(CH3CN)3}2{μ-SCHCHCH(OCH2C⋮CCH3)S}](CF3SO3)4 (7), respectively. The reaction of 1 with diols, (HO)CHRC⋮CCHR(OH), gave furyl complexes, [{Ru(P(OCH3)3)2(CH3CN)3}2{μ-SSCCROCRCH}](CF3SO3)3 (8:  R = H, 9:  R = CH3) via intramolecular elimination of a H2O molecule and a H+. Even though (HO)(H3C)2CC⋮CC(CH3)2(OH) does not have any propargylic C−H bond, it also reacts with 1 to give [{Ru(P(OCH3)3)2(CH3CN)3}2{μ-SCH2C(CH2)C(CC(CH3)2)}S](CF3SO3)4 (10). In addition, the reaction of 1 with (CH3O)(H3C)2CC⋮CC(CH3)2(OCH3) gives [{Ru(P(OCH3)3)2(CH3CN)2}{μ-SC(C(CH3)2OCH3)CCC(CH3)CH2S}{Ru(P(OCH3)3)2(CH3CN)3}](CF3SO3)4 (11), in which one molecule of CH3OH is eliminated, and the S−S bond is cleaved.