Modular Functionalization of Allenes to Aminated Stereotriads

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...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2012-07, Vol.134 (26), p.10807-10810
Main Authors: Adams, Christopher S., Boralsky, Luke A., Guzei, Ilia A., Schomaker, Jennifer M.
Format: Article
Language:English
Subjects:
Alkenes - chemistry
Amination
Aziridines - chemical synthesis
Catalysis
Organometallic Compounds - chemistry
Oxidation-Reduction
Rhodium - chemistry
Stereoisomerism
Sulfonic Acids - chemistry
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Summary: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.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja304859w