Description:
<jats:title>Abstract</jats:title><jats:p>A strategy for the vanadium‐catalyzed dehydrative C‐ and S‐alkylation by nucleophilic substitution of benzhydrols with arenes and thiols is reported. The alkylation was achieved with the divanadium oxoperoxo complex [K<jats:sub>3</jats:sub>(V<jats:sup>+5</jats:sup>)<jats:sub>2</jats:sub>(O<jats:sub>2</jats:sub><jats:sup>2−)</jats:sup><jats:sub>4</jats:sub>(O<jats:sup>2−</jats:sup>)<jats:sub>2</jats:sub>(<jats:italic>μ</jats:italic>‐OH)] in water under air. The newly developed transformation could accommodate a broad substrate scope, including (hetero)arenes and thiols (34 examples). Both the symmetrical and unsymmetrical benzhydrols furnished excellent yields of the alkylated product under mild reaction conditions. The scope of this strategy was further extended to synthesize<jats:italic>bis</jats:italic>‐benzylated arenes (poly‐arylated products) in high yields and regioselectivities. The green metrics determination of all the alkylated products suggests the technical and environmental benefits of the present protocol. The longevity experiment reveals the catalytic activity was maintained over seven cycles. To understand the mechanism of the present reaction, spectroscopic and kinetic studies were undertaken. This simple protocol, which affords the desired products with water as the by‐product, can be achieved under mild conditions without needing a base or other additives.</jats:p>