Carbon monoxide is one of the most important C1 molecules in organic chemistry. Many novel procedures for its conversion have been developed, and some have even been industrialized. In this review, we discuss and categorize CO chemistry into four classes: (1) transition-metal-mediated carbonylation, (2) strong-acid-initiated cationic carbonylation, (3) anionic carbonylation, and (4) free-radical carbonylation. Relevant achievements are selected and discussed in detail.

Thiocarbonylation of alkenes offers an ideal procedure for the synthesis of thioesters. However, thiocarbonylation of alkenes, especially styrenes, to produce valuable linear thioesters has remained a challenge. In this Letter, a general palladium-catalyzed thiocarbonylation of alkenes to produce linear thioesters has been achieved. Moderate to good yields of desired thioesters can be produced from readily available alkenes in a straightforward manner.

A procedure on palladium-catalyzed selective aminocarbonylation of styrenes with nitroarenes for the synthesis of α,β-unsaturated amides has been developed. A range of substituted α,β-unsaturated amides were synthesized in moderate to good yields. Interestingly, nitroarenes act as both a nitrogen source and oxidant, and Mo(CO) acts as a solid CO source and reductant in this catalytic system.

Transition-metal-catalyzed multi-component carbonylation represents an efficient strategy for the preparation of various functionalizedc arbonyl-containing compounds. Herein, we report ag eneral palladium-catalyzed perfluoroalkylative carbonylation of unactivated alkenes using inexpensive and readily available carbon monoxide as the C1 source and perfluoroalkyl halides as the coupling partner.Awide range of phenols and alcohols were transformed into the corresponding b-perfluoroalkyl esters in high yields with broad functional group tolerance and good chemoselectivity.A dditionally,alkylhalides can be utilized as alkoxy source as well to give the desired esters.M oreover,s everal pharmaceutical and bio-active molecules were also suitable substrates for this onepot multi-component carbonylation process to give the targeted products in good yields.

The carbonylative coupling of aryl halides with unactivated alkenes remains a challenge, because of the low reactivity of acyl-palladium intermediate to the olefins. In this paper, a palladium-catalyzed carbonylative coupling/amination of aryl iodides with unactivated alkenes for the synthesis of βaminoketone derivatives has been developed. With the assistance of a directing group (8-aminoquinoline, AQ), the coordination of the olefin to acyl-palladium complex can be enhanced, thereby promoting the acylpalladation across the CC double bonds. A broad range of β-aminoketone derivatives were prepared in moderate to excellent yields with complete regioselectivity by using 4-pentenoic and 2-vinylbenzoic amide derivatives as the starting materials. This methodology involves the formation of two C−C bonds as well as one C−N bond, and provided a method for the carbonylative difunctionalization of unactivated alkenes.

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A copper-catalyzed alkoxycarbonylation transformation of unactivated alkyl iodides has been developed. Various alkyl iodides can be converted into the corresponding tert-butyl esters in good yields. NaO t Bu acts as both a nucleophile and a base. Moreover, other types of aliphatic esters can also be obtained in moderated yields if extra alcohols are added. Both primary and secondary alkyl alcohols can react successfully.

In this Letter, a palladium-catalyzed multicomponent procedure for the selective synthesis of α-substituted α,β-unsaturated ketones has been developed. With readily available allenes, arylboronic acids, and nitroarenes as the substrates, the reaction proceeds selectively to the desired α-substituted enones. Notably, no manipulation of carbon monoxide gas is needed here, and Mo­(CO)6 has been applied as a stable solid CO source instead. Additionally, as an oxidative coupling reaction, nitroarenes are used as both the amine source and the oxidant to regenerate the active palladium species.