title: Reactions of ruthenium Cp phosphine complex with 4,4-disubstituted-1,6-enynes: effect of methyl substituents in the olefinic fraction.
abstract: We studied chemical reactions of Cp(PPh(3))(2)RuCl with nine 1,6-enyne compounds (1-4, 8, 12, 19, 21, and 22) in which the triple bond is associated with propargylic alcohol and the olefinic group has various substituted methyl groups. For the enyne compounds 1-3 with no substituted methyl group, the reaction takes place at the propargylic alcohol first giving the allenylidene complex 6 which could undergo a skeletal rearrangement to yield the disubstituted vinylidene complex 7. By changing the propargylic alcohol to propargylic ether, the reaction gives the carbene complex 10 as the major product and the butadiene complex 9 by a cyclization reaction as the minor product. For enyne 12 with two methyl groups at the terminal carbon of the olefinic part, formation of either of the carbene complexes 15 and 16 with a substituted cyclopentenyl ring at Calpha or the vinylidene complex 17 is controlled by the use of solvent. For the formation of 15 and 16, a C-C bond-forming cyclization reaction is proposed to occur at Cbeta in an intermediate where the triple bond is pi-coordinated. However, for the vinylidene intermediate, the reaction may proceed by the formation of the allenylidene, which undergoes a retro-ene reaction to bring about cleavage of the dimethyl substituted allyl group giving 17. For two enynes 21 and 22 where each olefinic portion is internally substituted with one methyl group, two vinylidene complexes 23 and 24 each with a five-membered ring bonded at Cbeta are isolated. The reaction proceeds via formation of an allenylidene intermediate followed by a cyclization at Cgamma. Stabilization of the cationic charge by the presence of methyl subsituents clearly controls the reaction pathway to give different products. These chemical reactions and their mechanisms are corroborated by structure determinations of five ruthenium complexes using single crystal X-ray diffraction analysis.
authors: Department of Chemistry, National Taiwan University, Taipei, Taiwan 106, Republic of China.
authors: Chia-Pei
authors: CP
authors: Chung
authors: Chien-Chih
authors: CC
authors: Chen
authors: Ying-Chih
authors: YC
authors: Lin
authors: Yi-Hong
authors: YH
authors: Liu
authors: Yu
authors: Y
authors: Wang