Photocatalytic Redox-Neutral Alkoxyacylation of Alkenes

β-Alkoxyketones are important building blocks in organic synthesis. By utilizing CBZ6, with an oxidative potential of −2.16 V (vs the saturated calomel electrode), as a redox-neutral photocatalyst, alkoxyacylation of olefins was accomplished under the irradiation of visible light via a cationic intermediate. It involves the addition of an acyl radical to olefin to form a radical intermediate and the following oxidation of the radical intermediate to the benzyl cationic intermediate that is captured by alkoxy anions. This process provides concise and practical access to the β-functionalized ketones.