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Abstract
The C-C bond activation allows direct reconstruction of organic framework. However, it has not been explored in atroposelective de novo synthesis of biaryls, and prior studies are predominantly limited to employment of alcohols with a preinstalled chiral axis. Described here is Ni(0)/PYBOX-catalyzed de novo construction of chiral axis via asymmetric C-C coupling of benzotriazinones and benzocyclobutenols, which proceeded under mild conditions with excellent enantioselectivity to give biaryls with multifunctional groups. The reactivity was enabled by N-N and C-C activation with dual ring scission as a driving force. A combination of experimental and computational studies revealed details of the catalytic mechanism. Key steps include N-N oxidative addition of the benzotriazinones to give a stable nickelacycle. Subsequent -carbon elimination of the ligated benzocyclobutenol is turnover-limiting, and the product is delivered from the enantio-determining C-C reductive elimination
Supplementary materials
Title
Atroposelective de novo Access to Biaryls via Nickel-Catalyzed C-C Activation of Benzocyclobutenols: Aryl Sources Powered by Dual Ring Scissions
Description
Described here is Ni(0)/PYBOX-catalyzed de novo construction of chiral axis via asymmetric C-C coupling of benzotriazinones and benzocyclobutenols, which proceeded under mild conditions with excellent enantioselectivity to give biaryls with multifunctional groups. The reactivity was enabled by N-N and C-C activation with dual ring scission as a driving force. A combination of experimental and computational studies revealed details of the catalytic mechanism. Key steps include N-N oxidative addition of the benzotriazinones to give a stable nickelacycle. Subsequent -carbon elimination of the ligated benzocyclobutenol is turnover-limiting, and the product is delivered from the enantio-determining C-C reductive elimination.
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