Intermolecular Dehydrative Coupling and Intramolecular Cyclization of Ruthenium Vinylidene Complexes Formed from Aromatic Propynes Containing Carbonyl Functionalities.

ABSTRACT

A remarkable intermolecular dehydrative coupling reaction with the formation of a C-C bond was found for the vinylidene complex 2 a, yielding the dinuclear bisvinylidene complex 4 a. Complex 2 a containing 1-hydroxyindan moiety was first formed from the reaction of o-propynyl benzaldehyde 1 a with [Ru]-Cl ([Ru]=Cp(PPh3 )2 Ru) by a cyclization process. For analogous aldehyde 1 b containing an additional 1,3-dioxolane group on the aryl ring, similar intermolecular coupling yields the dinuclear bisvinylidene complex 4 b. However, the fluoro group on the aryl ring in aldehyde 1 c inhibits the coupling reaction, giving only the vinylidene complex 2 c. For the reactions of [Ru]-Cl in MeOH with compounds 1 f, 1 g and 1 h, each with a ketone functionality, cyclization gives vinylidene complexes 2 f, 2 g and 2 h, respectively. However, no similar intermolecular coupling was observed, instead, the intramolecular dehydration yields 8 f, 8 g and 8 h, respectively. In CDCl3 , catalytic cyclization is observed for the o-propynylphenyl ketone 1 h with [Ru]-Cl at 50 °C giving the isochromene products 14 h. Furthermore, treatment of the o-propynylaryl α,ß-unsaturated ketones 1 k-m and 1 n with [Ru]-Cl in MeOH affords the corresponding vinylidene complexes 10 k-m and 11 n each with 1-benzosuberone moiety in the presence of NH4 PF6 . These intramolecular cyclization products were formed by the addition of Cß onto the terminal carbon of the alkene moiety. All these reaction products were characterized by spectroscopic methods. In addition, structures of complexes 4 a, and 10 l were confirmed by single crystal X-ray diffraction analysis.