A General and Convenient Method for the Rhodium‐Catalyzed Decarbonylation of Aldehydes

Abstract

A practical protocol for the decarbonylation of a wide range of aldehydes has been developed by using commercially available RhCl 3 ·3 H 2 O and dppp in a diglyme solution. This method gives rise to decarbonylated products in good to high yield and is particularly useful because of its experimental simplicity, high generality and excellent level of functional group tolerance. The reaction has been applied in a tandem Oppenauer oxidation-decarbonylation sequence, which removes a hydroxymethyl group in one operation.

Rh-catalyzed C–C bond cleavage by transfer hydroformylation

“…Over the past fifty years, activating aldehyde C–H bonds with Rh has been thoroughly investigated (12); however, the resulting acyl–Rh III –hydrides have been trapped mainly by hydroacylation (13) and/or decarbonylation (14,15). This common intermediate is also implicated in hydroformylation, which is practiced on an industrial scale using syngas (16).…”

Recent Biomimetic and Organocatalytic Syntheses of ?-Tocopherol

“…Reduction of the acid 38 followed by oxidation gave the aldehyde 39 in 75% yield. Subsequent Rh-catalyzed decarbonylation [18] furnished the tocopherol ether 30 in 80% yield, 93% de. The same compound was obtained from 38 in 72% yield, 94% de using a Barton decarboxylation procedure.…”

Ruthenium‐Catalyzed Alkene Synthesis by the Decarbonylative Coupling of Aldehydes with Alkynes

“…[1] There are now many examples of catalytic variants of the decarbonylation of an aldehyde 1 to give the decarbonylated product 2 (Scheme 1 a). Recent examples include the use of RhCl 3 ·3 H 2 O with Ph 2 PCH 2 CH 2 CH 2 PPh 2 in diglyme at reflux [2] and [{Ir(cod)Cl} 2 ] with PPh 3 in dioxane at reflux. [3] These reactions are believed to proceed by oxidative addition of the catalyst into the CÀH bond of the aldehyde and fragmentation of the acyl group to give intermediate 3.…”