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Intramolecular C(sp3)[BOND]N Coupling by Oxidation of Benzylic C,N-Dianions


  • We thank Dr. Vishnumaya Bisai (IISER Bhopal), Dr. André Isaacs (College of the Holy Cross (USA)), and Erica D’Amato (visiting undergraduate Amgen Scholar, 2011) for assistance with the preparation of starting materials for an initial study. This work was supported by the NIH-USA (NIGMS RO1 GM86374) and a Research Scholar Grant from the American Cancer Society-USA (RSG-09-017-01-CDD to R.S.). R.S. is a Camille Dreyfus Teacher Scholar. J.L.J. is grateful to the NSF for a graduate fellowship. E.S.B was supported by a Chemical Biology Interface Training Grant from the NIH (T32 GM066698). We are grateful to Eli Lilly, Abbott, and Roche for unrestricted financial support.


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What a couple! An intramolecular, C(sp3)[BOND]N coupling to afford azacycles is reported. This reaction proceeds through the oxidation of benzylic C,N-dianions with iodine and builds on an earlier discovery during the synthesis of the natural product lyconadin A. The current study employs conformationally unbiased substrates with less acidic C[BOND]H bonds and less reactive nitrogen nucleophiles. ZnCl2 was identified as an important additive.