Visible Light‐Driven Pd‐Catalyzed Carbonylative C(sp ³ )–H Functionalization at Room Temperature and 1 Bar of CO Gas

The direct carbonylation of C(sp 3 )─H bonds is a powerful strategy to transform readily available, unfunctionalized materials into diverse, value‐added functionalities. However, these reactions often require forcing conditions, such as high temperatures and high CO gas pressures, in the presence of peroxide oxidants. In this study, we report a practical C(sp 3 )─H carbonylation method that operates under photoexcited conditions at room temperature with only 1 bar of CO gas, utilizing an aryl bromide as a pseudo‐oxidant and a HAT precursor to bypass traditional exogenous oxidants. These mild conditions parameters enable the use of a simple vial‐based setup, effectively obviating the need for cumbersome pressurized vessels during the photochemical process. The reaction proceeds smoothly with benzylic C−H and unactivated C(sp 3 )─H bonds, affording esters in good to excellent yields. Moreover, a one‐pot procedure is also developed for the synthesis of amides, acids, thioesters, and an ester derivative of an indole alkaloid, directly from C−H bonds, further demonstrating the practical utility of this methodology.