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An extremely efficient cobalt catalyst for the hydroboration of both vinylarenes and aliphatic α-olefins with pinacolborane is described, providing the anti-Markovnikov products with excellent regio- and chemoselectivity, broad functional-group tolerance, and high turnover numbers (up to 19,800). The alkene hydroboration route is further extended to a two-step, one-pot hydroboration and cross-coupling of alkylboronates with aryl chlorides.
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