Abstract

The highly chemo-, enantio-, and diastereoselective catalyst-controlled intramolecular allylic C-H insertion and cyclopropanation of donor/donor carbenes are reported. The RuII /Pybox complex selectively catalyzed the intramolecular allylic C-H insertion, providing vinyl-substituted dihydroindoles with greater than 20:1 chemoselectivity and up to greater than 99 % ee. Chiral dirhodium(II) tetracarboxylates, however, selectively promoted the intramolecular cyclopropanation, giving rise to cyclopropane-fused tetrahydroquinoline derivatives in excellent yields with greater than 99:1 chemoselectivity and up to 97 % ee.

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