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Dehydration reaction of hydroxyl substituted alkenes and alkynes on the Ru(2)S(2) complex
Kazuko Matsumoto1, Yoshihiro Moriya, Hiroyasu Sugiyama
1Department of Chemistry, School of Science and Engineering, and Advanced Research Institute of Science and Engineering, Waseda University and Japan Science and Technology Corporation, 3-4-1 Ohkubo, Shinjuku, Tokyo 169-8555, Japan. kmatsu@waseda.jp
Abstract:
A variety of inter- and intramolecular dehydration was found in the reactions of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)(mu-S(2))](CF(3)SO(3))(4) (1) with hydroxyl substituted alkenes and alkynes. Treatment of 1 with allyl alcohol gave a C(3)S(2) five-membered ring complex, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)CH(2)CH(OCH(2)CH=CH(2))S]](CF(3)SO(3))(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 C(4)S(2) six-membered ring complex, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2) [mu-SCH(2)CH=CHCH(2)S]](CF(3)SO(3))(4) (3). Complex 1 reacts with 2-propyn-1-ol or 2-butyn-1-ol to give homocoupling products, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCR=CHCH(OCH(2)C triple bond CR)S]](CF(3)SO(3))(4) (4: R = H, 5: R = CH(3)), via intermolecular dehydration. In the reaction with 2-propyn-1-ol, the intermediate complex having a hydroxyl group, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH=CHCH(OH)S]](CF(3)SO(3))(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(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH=CHCH(OCH(2)C triple bond CCH(3))S]](CF(3)SO(3))(4) (7), respectively. The reaction of 1 with diols, (HO)CHRC triple bond CCHR(OH), gave furyl complexes, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SSC=CROCR=CH]](CF(3)SO(3))(3) (8: R = H, 9: R = CH(3)) via intramolecular elimination of a H(2)O molecule and a H(+). Even though (HO)(H(3)C)(2)CC triple bond CC(CH(3))(2)(OH) does not have any propargylic C-H bond, it also reacts with 1 to give [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)C(=CH(2))C(=C=C(CH(3))(2))]S](CF(3)SO(3))(4) (10). In addition, the reaction of 1 with (CH(3)O)(H(3)C)(2)CC triple bond CC(CH(3))(2)(OCH(3)) gives [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(2)][mu-S=C(C(CH(3))(2)OCH(3))C=CC(CH(3))CH(2)S][Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)]](CF(3)SO(3))(4) (11), in which one molecule of CH(3)OH is eliminated, and the S-S bond is cleaved.
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