4440-28-2Relevant academic research and scientific papers
Reactions of diazo compounds with alkenes catalysed by [RuCl(cod)(Cp)]: Effect of the substituents in the formation of cyclopropanation or metathesis products
Basato, Marino,Tubaro, Cristina,Biffis, Andrea,Bonato, Marco,Buscemi, Gabriella,Lighezzolo, Filippo,Lunardi, Pamela,Yianini, Chiara,Benetollo, Franco,Del Zotto, Alessandro
experimental part, p. 1516 - 1526 (2009/09/04)
The reaction of diazo compounds with alkenes catalysed by complex [RuCl(COd)(Cp)] (cod = 1, 5-cyclooctadiene, Cp = cyclopentadienyl) has been studied. The catalytic cycle involves in the first step the decomposition of the diazo derivative to afford the reactive [RuCl(Cp)I=C(R1)R 2)] intermediate and a mechanism is proposed for this step based on a kinetic study of the simple coupling reaction of ethyl diazoacetate. The evolution of the Ru-carbene intermediate in the presence of alkenes depends on the nature of the substituents at both the diazo N2=C(R 1)R2 (R1, R2 = Ph, H; Ph, CO 2Me; Ph, Ph; C(R1)R2 = fluorene) and the olefin substrates R3(H)C= C(H)R4 (R3, R4 = CO2Et, CO2Et; Ph, Ph; Ph, Me; Ph, H; Me, Br; Me, CN; Ph, CN; H, CN; CN, CN). A remarkable reactivity of the complex was recorded, especially towards unstable aryldiazo compounds and electron-poor olefins. The results obtained indicate that either cyclopropanation or metathesis products can be formed: the first products are favoured by the presence of a cyano substituent at the double bond and the second ones by a phenyl.
