Pd-catalyzed carbonylative access to aroyl phosphonates from (hetero)aryl bromides

Abstract

The first transition-metal catalysed carbonylation with a phosphorus nucleophile is presented. This transformation provides efficient and mild access to aroylphosphonates under mild conditions, thus ensuring a broad substrate scope. The utility of aroylphosphonates as useful reagents, capable of participating in a number of transformations, is subsequently demonstrated. Furthermore, access to [(13)C]-carbonyl labelled aroylphosphonates is easily realised for the first time, as only a near stoichiometric amount of CO is required applying this carbonylation.

Recent developments in carbonylation chemistry using [13C]CO, [11C]CO, and [14C]CO

“…Recently, the first example of carbonylation using a phosphorous‐based nucleophile was reported. An example (compound 50 ) of this unusual coupling combined with [ 13 C ]CO is shown in Scheme for the generation of acyl phosphonates …”

“…An example (compound 50) of this unusual coupling combined with [ 13 C ]CO is shown in Scheme 12 for the generation of acyl phosphonates. 44…”

Computational Exploration of Mechanistic Avenues in C–H Activation Assisted Pd-Catalyzed Carbonylative Coupling

“…It was believed that the reaction proceeds via in situ formation of catalytically active highenergy aroyl triflate electrophiles. 29 Since 2010, the group of Skrydstrup has made significant contribution in development of reactions involving metalcatalyzed carbonylative couplings to generate aroyl phosphonates, 30 α-arylated nitromethanes, 31 benzyl alkyl ketones, 32 βketoamides, and β-ketoesters. 33,34 Very recently, they have shown the first example of intermolecular Pd-catalyzed carbonylative coupling of aryl bromides relying on C−H activation, as presented in Scheme 1.…”

“…Since 2010, the group of Skrydstrup has made significant contribution in development of reactions involving metal-catalyzed carbonylative couplings to generate aroyl phosphonates, α-arylated nitromethanes, benzyl alkyl ketones, β-ketoamides, and β-ketoesters. , Very recently, they have shown the first example of intermolecular Pd-catalyzed carbonylative coupling of aryl bromides relying on C–H activation, as presented in Scheme . Importantly, this transformation occurs efficiently at moderate reaction temperatures and does not require strong base or other reactive species.…”

Controlled Release of Carbon Monoxide from a Pseudo Electron-Deficient Organometallic Complex

“…The toxicity of carbon monoxide makes the utilization of CO cylinders difficult for small-scale reactions in laboratories, and the purchase and handling of such cylinders are strictly regulated. Therefore, there has been a long and significant academic and industrial interest in the development of materials capable of reversibly capturing and releasing CO. − A number of CO surrogates which can avoid the utilization of CO gas cylinders have been developed by Skrydstrup and co-workers − and others. − However, this is still an extremely challenging quest owing to the difficulty to desorb the ligand from existing carbon monoxide-containing materials, − without irreversibly damaging them …”