Recent advances in the carbonylative synthesis of heterocycles by using diverse CO surrogates as sources of CO are summarized and discussed.

General comments, general procedure, optimization details, analytic data, and NMR spectra PDF)Accession Codes CCDC 2010044 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_

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.