Journal of the American Chemical Society 2012-07-04

Modular functionalization of allenes to aminated stereotriads.

Christopher S Adams, Luke A Boralsky, Ilia A Guzei, Jennifer M Schomaker

Index: J. Am. Chem. Soc. 134(26) , 10807-10, (2012)

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Abstract

Nitrogen-containing stereotriads, compounds with three adjacent stereodefined carbons, are commonly found in biologically important molecules. However, the preparation of molecules bearing these motifs can be challenging. Herein, we describe a modular oxidation protocol which converts a substituted allene to a triply functionalized amine of the form C-X/C-N/C-Y. The key step employs a Rh-catalyzed intramolecular conversion of the allene to a strained bicyclic methylene aziridine. This reactive intermediate is further elaborated to the target products, often in one reaction vessel and with effective transfer of the axial chirality of the allene to point chirality in the stereotriad.