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Heteroatoms are essential to living organisms and present in almost all molecules with medicinal usage. The catalytic functionalization at the carbon‐centered radical with an adjacent heteroatom provides an effective way to value added moiety while retaining the unique physicochemical and pharmacological properties of heteroatoms, which can promote the development of pharmaceutical and fine chemical production. Carbonylative transformation was discovered nearly a century ago which is an efficient method for the synthesis of carbonyl‐containing molecules with potent applications in both industry and academia. Despite numerous advances in new reaction development, carbonylative transformation involving adjacent heteroatom carbon radical remain a subject that deserves to be discussed. In this minireview, we systematically summarized and discussed the recent advances in carbonylative transformations involving carbon‐centered radicals with an adjacent heteroatom, including oxygen (O), nitrogen (N), phosphorus (P), silicon (Si), sulfur (S), boron (B), fluorine (F), and chlorine (Cl). The related reaction mechanism was also discussed. [ABSTRACT FROM AUTHOR]

Carbonylative multi‐component reactions (CMCR), having four or more kinds of starting materials, provide an efficient strategy for the preparation of polyfunctional carbonylated compounds. Diverse CMCR utilizing non‐noble transition‐metal catalysts have been developed. This review summarized and discussed the recent advances in non‐noble metal‐catalyzed carbonylative multi‐component reactions. [ABSTRACT FROM AUTHOR]

A procedure on palladium‐catalyzed carbonylative reaction of trifluoroacetimidoyl chlorides and nitro compounds for the construction of pharmaceutically valuable 2‐(trifluoromethyl)quinazolin‐4(3H)‐ones has been achieved. In this transformation, Mo(CO)6 has been used both as a convenient CO source and a reducing reagent. This newly developed protocol is compatible with various nitro compounds and can be readily scaled up to 1 mmol scale. [ABSTRACT FROM AUTHOR]

A low cost FeCl3‐mediated cascade annulation of trifluoroacetimidoyl chlorides and hydrazides for the efficient synthesis of 5‐trifluoromethyl‐1,2,4‐triazoles has been developed. The transformation proceeds through a cascade base‐promoted intermolecular C−N bond formation and FeCl3‐mediated intramolecular dehydration sequence under mild conditions. The protocol exhibits many notable features and can be readily scaled up to gram scale. [ABSTRACT FROM AUTHOR]

Herein, a new reaction for the site-selective carbonylation of arenes via C(sp 2 )-H thianthrenation under mild conditions has been developed. With low loadings of palladium catalysts, various desired 1,2-diarylethanones are produced in good yields. This strategy also enables the late-stage modification of complex molecules, which was previously challenging with similar carbonylative Negishi-type reactions., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Multi-component carbonylation of olefins, a reaction that installs both a carbon-carbon(heteroatom) bond and a carbonyl group across the double bond, is an attractive strategy for alkene functionalization. Herein, we developed a novel nickel-catalyzed four-component carbonylation of olefins with ethers under low CO gas pressure. Using alcohols and amines as the reaction partner, diverse γ-oxy-substituted esters and amides were produced in good yields with excellent functional group tolerance. Notably, Naftidrofuryl, a medicine for the treatment of cerebrovascular disease (CVD), can be synthesized by this process straightforwardly., (© 2022 Wiley-VCH GmbH.)

A palladium-catalyzed desulfonative carbonylation of thiosulfonates has been explored. Without any additive, a series of S -aryl/alkyl benzenesulfonothioates were successfully transformed to thioesters in moderate to excellent yields by SO 2 extrusion and CO insertion under the pressure of 1 bar of CO. The solvent dimethylacetamide (DMAc) facilitated this desulfonative carbonylation due to its high absorbing ability of SO 2 .

Ethers are of central importance in the fields of biomass, energy, and organic chemistry. Herein, a novel cobalt-catalyzed carbonylative coupling of ethers with amines to construct α-carbonylated ethers has been achieved. Remarkably, Alfuzosin, a medicine for treatment of benign prostatic hyperplasia (BPH), can be synthesized by this process straightforwardly. Notably, this protocol presents the first example on the direct carbonylative reaction of ethers., (© 2022 Wiley-VCH GmbH.)

An FeCl 3 -mediated cascade coupling/decarbonylative annulation reaction for the efficient construction of 2-(trifluoromethyl)quinazolin-4(3 H )-ones has been developed. This transformation employs readily available isatins and trifluoroacetimidoyl chlorides as the starting materials, providing a facile and practical route to diverse biologically relevant quinazolin-4(3 H )-one derivatives. A plausible reaction pathway has been proposed based on the mechanistic observations.