Aerobic Dehydrogenative Heck Reaction of Ferrocene with a Pd(OAc)₂/4,5-Diazafluoren-9-one Catalyst

Abstract

The aerobic dehydrogenative Heck alkenylation of ferrocene with alkenes, catalyzed by a Pd(OAc)2/4,5-diazafluoren-9-one system, is disclosed. Monoalkenylated ferrocenes were obtained in moderate yields and selectivities using various electron-poor alkenes. Oxygen at an atmospheric pressure was the sole oxidant. The reaction can be carried out at room temperature (several days) or at 70 °C (∼3 h).

Synthesis, regioselective aerobic Pd(ii)-catalyzed C–H bond alkenylation and the photophysical properties of pyrenylphenylpyrazoles

“…We performed alkenylation of 2a with n-butyl acrylate under conditions we had described earlier for alkenylation of ferrocene and pyrene. [30][31][32] The reaction was conducted in boiling acetic acid under oxygen (1 atm) in the presence of a catalytic amount (5 mol%) of Pd(OAc) 2 and 4,5-diazafluoren-9-one (DAF, 10 mol%) (Scheme 2).…”

Recent advances in transition metal-catalyzed C–H bond functionalization of ferrocene derivatives

“…Rooted in stoichiometric work on alkenylation of ferrocene by 35 Fujiwara and co-workers, 27 the palladium-catalyzed aerobic dehydrogenative Heck reaction of ferrocene was recently demonstrated by Zakrzewski and co-workers (Scheme 17). 28 In this process, the use of 4,5-diazafluoren-9-one (DAF) as additive resulted essential to boost product formation. It is also worth 40 noting that the reaction required molecular oxygen as the sole oxidant.…”

Transfer hydrogenation of aryl ketones with homogeneous ruthenium catalysts containing diazafluorene ligands

“…[21][22][23][24][25][26][27][28] Nevertheless, the applications of such complexes in catalytic reactions are limited. [29][30][31][32][33] Compared with other hydrogenation techniques such as using molecular hydrogen, catalytic transfer hydrogenation reactions are characterised by an environmentally benign synthetic process and contribute to industrial applications. [34,35] Catalytic reduction of unsaturated compounds via transfer hydrogenation is one of the most reliable methods of obtaining the corresponding saturated products which are versatile synthetic precursors that yield further functionalised molecules.…”