Toward Sustainable Carbonylation Reactions Enabled by CO Surrogates in Green Solvents

Carbonylation reactions represent a powerful strategy in synthetic chemistry, because they enable the straightforward incorporation of carbonyl functionalities into organic substrates through transition‐metal catalysis in the presence of various nucleophiles. Traditionally, these transformations have been conducted under high pressures of carbon monoxide (CO), a lethal gas, and have relied on volatile organic solvents (VOCs) that are often toxic and derived from petroleum resources, thereby raising significant environmental and safety concerns. In line with the principle of green chemistry, this review summarizes recent advances in carbonylation reactions based on organic and inorganic CO surrogates that safely generate CO on demand within the reaction system, with a specific focus on strategies combining safer CO sources and green solvents classified as more sustainable alternatives to conventional VOCs according to the GSK solvent selection guide.