failed to improve the yield (see supporting information S1). The thermal-activation was found to be unique with the combination of Zn and di-tert-butyl peroxide (DTBP), as using either metallaphotoredox or different reductants did not yield the desired product (entry 5). Different peroxides have also been tested under this dehydrogenative coupling manifold, and DTBP, a stable organic peroxide, performed the best (see supporting information S3). The use of silyl chlorides only yielded the silylated pinacol-coupled byproducts (entry 6). whereas 2.0 equiv. of water resulted in product 3a in an improved 62% isolated yield (entry 7). Conducting the reaction in darkness resulted in a similar yield, excluded the possibility of photo-activation (entry 8).