Palladium-Catalyzed Carbonylative Transformation of C(sp³)–X Bonds

Abstract

During the last 50 years, the palladium-catalyzed carbonylation reactions underwent continuous development. Apart from carbonylation of aromatic (pseudo)-halide and alkene (C-sp2) compounds, the use of C­(sp3)–X compounds such as allyl compounds, benzyl compounds, and aliphatic alkanes have become the most useful tool for the synthesis of β,γ-unsaturated carbonyl compounds, aliphatic carboxylic acid, and their derivatives. The recently budding development in the area of palladium-catalyzed C­(sp3)–X (especially X = H) activation makes us feel it necessary to file a summary on the past, current contributions, and a prospective outlook on the palladium-catalyzed carbonylative transformation of C­(sp3)–X bonds, which is the focus of this review.

Cobalt-Catalyzed Silylcarbonylation of Unactivated Secondary Alkyl Tosylates at Low Pressure

“…1 Recent studies have developed carbonylations 2 and carboxylations 3 of alkyl electrophiles, which have been much less studied than aryl or vinyl substrates. These catalytic transformations are proposed to involve radical intermediates produced from the activation of alkyl halide substrates.…”

Low‐Pressure Radical 11C‐Aminocarbonylation of Alkyl Iodides through Thermal Initiation

“…There are also a few examples of compounds obtained from multi‐step synthesis starting with 11 C‐carbonylation; these include 11 C‐labelled hydroxamic acid from esters, and alkyl iodides, from aldehydes/carboxylic acids through olefin carbonylation. However, palladium‐mediated carbonylation is restricted to organic halides lacking beta‐hydrogen atoms; methyl, aryl, benzyl, and alkenyl iodides are good examples of such species , . This limitation can potentially be overcome by the recent 11 C‐carbonylative cross‐coupling of alkyl iodides containing beta‐hydrogen atoms and amines by using air‐sensitive Ni(COD) 2 with bathophenanthroline as a supporting ligand .…”

Transition Metal-Catalyzed Carbonylative CH Bond Functionalization of Arenes and C(sp3)H Bond of Alkanes

“…The variation of the number of fluorine atoms on the polyfluoroarene was studied, and the product yield drops as the number of fluorine atoms are replaced by hydrogen atoms or alkyl groups. The protocol was also used for the synthesis of 13 C-labelled benzopolyfluorophenone, which in turn, was used for the synthesis of a labelled potent nitric oxide synthases (NOS) inhibitor. The mechanism proposed involves the oxidative insertion of the aryl bromide to Pd(0), followed by coordination and insertion of CO, to give the acylpalladium complex 64.…”

“…[7,11] Carbonylative CAH activation of arenes and alkanes has also been touched upon. [12,13] But to the best of our knowledge, an exhaustive review, focusing on the carbonylative CAH functionalization of arenes and alkanes, with and without directing groups, and the use of CO surrogates with mechanistic details, is still lacking for the same. Hence, through this review, we aim to document and provide an insight into the carbonylative CAH functionalization of the above-mentioned substrates in a meticulous manner.…”