Pd–H from Pd/C and triethylamine: Implications in palladium catalysed reactions involving amines

Abstract

The palladium hydride-iminium complex generated from Pd/C and triethylamine catalyses the isomerisation of allylic alcohols into carbonyl compounds, and Pd/C catalyses the conjugate reduction of activated double bonds using triethylamine as the source of the two newly incorporated hydrogen atoms via the same complex.

Chemoenzymatic Synthesis of Idesolide from Benzoic Acid

“…Iron carbonyl complexes [Fe(CO) 5 , Fe 2 (CO) 9 , Fe 3 (CO) 12 ] were investigated under both thermal and photolytic conditions and led to the degradation of 6, mostly by rearomatization. 14 and palladium hydride, generated from Pd/C and triethylamine, 16 provided results similar to those observed with the ruthenium and iridium catalysts -slow conversion and degradation. Treatment of 6 with Grubbs first-generation catalyst (5 mol%, toluene, reflux) did provide enone 11 in 43% yield, as the only identifiable compound from a complex mixture (Scheme 4).…”

Catalytic properties of the Pd/C – triethylamine system

“…1) catalyses the isomerization of allylic alcohols into the corresponding carbonyl compounds, and that Pd/C catalyses the conjugate reduction of activated double bonds using triethylamine as the source of the two newly incorporated hydrogen atoms via the same complex. 9 A careful re-examination of these two reactions has revealed some Pd/C-catalyzed redox processes of allylic alcohols in the case of the isomerization reaction, and the in situ Pd/C-catalyzed production of ethylamine from Similar redox properties of palladium species have previously been observed. 14 In order to determine the origin of the redox products, we carried out some control experiments.…”

“…1-Cyclohexyl-2-propen-1-ol was prepared by addition of cyclohexyl carboxaldehyde to a THF solution of vinylmagnesium ketone. 26 The tricarbonyl(tropone)iron complex was prepared from tropone and Fe 2 (CO) 9 . 27 The substrate for entry 9 (Table 2) was prepared from the corresponding 1,6-enyne by a PausonKhand reaction.…”

Carbon–nitrogen bond activation of amines by rhodium(III) porphyrin complexes

“…Initially, Rh(ttp)Cl reacts with the weakest C(a)-H bond of amine to give 4 [22,23]. Subsequent b-hydride elimination of 4 produces Rh(ttp)H and an enamine.…”