Av isible-light-promoted photochemical protocol is reported for the coupling of aryldiazoacetates with boronic acids. This photochemical reactions hows great enhancement comparedt ot he same protocolp erformed in the absence of light. Except for af ew cases, the room temperature coupling in the dark (thermalp rocess) generally does not work. When it does, it is likely to also involve free carbenes as key intermediates. Alternatively,p hotochemical reactions show ab road scope,c an be performed under air and tolerate aw ide variety of functional groups.R eaction-evolution monitoring, DFT calculations and control experimentsh ave been used to evaluatet he main aspects of this intricate mechanistic scenario. Biologically activem olecules Adiphenine, Benactyzine and Aprophen have been prepared as examples of synthetic applications. Results and DiscussionAt the outset, we started our investigation employing aryldiazoacetate 1a and phenylboronic acid 2a,a iming at the preparationo fa,a-diphenyl ester 3a.I nitial screening of reaction Figure 1. Examples of biologically active a-branchede sters.

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Stereoelectronic effects were evaluated in the natural bond orbital framework as candidate sources of the preferred geometry of HOOR hydroperoxides. The reactivity of the compounds was also studied in terms of their HOMO–LUMO and O–O bond dissociation energies.

A room temperature protocol for the coupling between aryldiazoacetates and boronic acids is described, exhibiting limited scope in the dark, but being significantly improved under blue‐light irradiation. An intricate mechanistic scenario reveals common aspects for both processes, both relying on the generation of a key carbene intermediate, which attacks the boronic acid partner. These features are represented in the illustration by the yin yang symbol and the starships. More information can be found in the Full Paper by I. D. Jurberg et al. on page 5648.