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Chen, Jiawei; Vibbert, Hunter B; Yao, Chengbo; Bartholomew, Amymarie K; Aydt, Alexander P; Jockusch, Steffen; Norton, Jack R; Hammond, Matthew; Rauch, Michael (, Organometallics)
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Yao, Chengbo; Dahmen, Tobias; Gansäuer, Andreas; Norton, Jack (, Science)The opening of epoxides typically requires electrophilic activation, and subsequent nucleophilic (S N 2) attack on the less substituted carbon leads to alcohols with Markovnikov regioselectivity. We describe a cooperative catalysis approach to anti-Markovnikov alcohols by combining titanocene-catalyzed epoxide opening with chromium-catalyzed hydrogen activation and radical reduction. The titanocene enforces the anti-Markovnikov regioselectivity by forming the more highly substituted radical. The chromium catalyst sequentially transfers a hydrogen atom, proton, and electron from molecular hydrogen, avoiding a hydride transfer to the undesired site and resulting in 100% atom economy. Each step of the interconnected catalytic cycles was confirmed separately.more » « less