La-Catalyzed Decarbonylation of Formamides and Its Applications

Abstract

Herein we report the first catalytic decarbonylation and decarbonylative hydroamination of formamides without using additives enabled by a redox-neutral rare earth catalyst. The protocol displays complete N-aryl/alkenyl formamide-selectivity, thus providing a wide variety of creative uses of the N-formylation and N-deformylation method and opening up new prospects for minimizing waste and controlling the required selectivity in amine transformation events.

Controllable carbonyl-assisted C(sp3)–C(sp3) bond reduction and reorganization

“…Ln[N(SiMe 3 ) 2 ] 3 were elected as the precatalysts, as they are readily available and have previously exhibited a distinct performance in catalytic C–H bond activation. 22 After a systematic survey of reaction parameters, we were pleased to find that the reaction of 1a with one equivalent of DAMA ( DAMA = PhCH(OH)C 6 H 4 (OMe-4)) in toluene in the presence of 5 mol% Y[N(SiMe 3 ) 2 ] 3 ( Y-1 ) at 100 °C afforded the desired C(sp 3 )–C(sp 3 ) hydrogenolysis products 11 and 20a in 86% and 89% isolated yields, respectively (Tables S1 and S2†). Other rare-earth metals screened, such as La, Sm, and Lu, also afforded good results, although the reactions were carried out with Y-1 alone thereafter.…”

Manganese catalysed dehydrogenative synthesis of polyureas from diformamide and diamines

“…We speculate that under this condition formanilide can undergo decarbonylation to form aniline which could then react with isocyanate to form diphenylurea. 19,40 This could be an alternative pathway to the formation of homopolyurea in addition to the transformylation route proposed in Fig. 2.…”

Graphitic Carbon Nitride as Photocatalyst for the Direct Formylation of Anilines

“…The authors have cited additional references within the Supporting Information. [65][66][67][68][69][70][71][72][73]…”