Abstract
Insertion of a dimethyl acetylenedicarboxylate (DMAD) into the Ru-C bond in a cycloruthenated complex Ru[OC(6)H(3)(2-CH(2))(6-Me)-kappa(2)O,C](PMe(3))(4) () has been achieved to give a seven-membered oxaruthenacycle Ru[OC(6)H(3){2-CH(2)C(CO(2)Me)[double bond, length as m-dash]C(CO(2)Me)}(6-Me)-kappa(2)O,C](PMe(3))(3) () in 47% yield. The molecular structure of by X-ray analysis shows an agostic interaction between the ruthenium and one of the benzylic methylene protons. Complex shows fluxional behaviour in solution and the variable temperature NMR studies suggest this fluxionality to be responsible for the turnstile rotation of three PMe(3) ligands and the rotation of the alpha-methoxycarbonyl group. Heating of a toluene solution of at 100 degrees C for 2 h results in the 1,3-H shift reaction in to give a kappa(1)O,eta(3)-C,C',C'' allylic complex Ru[OC(6)H(3){2-CHC(CO(2)Me)CH(CO(2)Me)}(6-Me)-kappa(1)O,eta(3)C,C',C''](PMe(3))(3) () (80-90%), whose molecular structure is revealed by X-ray analysis. Acidolyses of and give 2-[(Z)-2',3'-bis(methoxycarbonyl)allyl]-6-methylphenol () (88%) and 2-[(Z)-2',3'-bis(methoxycarbonyl)propenyl]-6-methylphenol () (47%), respectively, and iodolyses of and produce 2,3-bis(methoxycarbonyl)-8-methyl-4H-benzopyran () (24%) and 2,3-bis(methoxycarbonyl)-8-methyl-2H-benzopyran () (48%), respectively.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.