Manganese-Catalyzed Oxidative Azidation of Cyclobutanols: Regiospecific Synthesis of Alkyl Azides by C-C Bond Cleavage

Rongguo Ren; Huijun Zhao; Leitao Huan; Chen Zhu

doi:10.1002/anie.201506578

Manganese-Catalyzed Oxidative Azidation of Cyclobutanols: Regiospecific Synthesis of Alkyl Azides by C-C Bond Cleavage

Angew Chem Int Ed Engl. 2015 Oct 19;54(43):12692-6. doi: 10.1002/anie.201506578. Epub 2015 Sep 1.

Authors

Rongguo Ren¹, Huijun Zhao¹, Leitao Huan¹, Chen Zhu^{2

3}

Affiliations

¹ Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu 215123 (China).
² Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu 215123 (China). chzhu@suda.edu.cn.
³ Key Laboratory of Synthesis Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, 345 Lingling Road, Shanghai 200032 (China). chzhu@suda.edu.cn.

PMID: 26331916
DOI: 10.1002/anie.201506578

Abstract

A novel, manganese-catalyzed oxidative azidation of cyclobutanols is described. A wide range of primary, secondary, and tertiary alkyl azides were generated in synthetically useful yields and exclusive regioselectivity. Aside from linear alkyl azides, otherwise elusive medium-sized cyclic azides were also readily prepared. Preliminary mechanistic studies reveal that the reaction likely proceeds by a radical-mediated C-C bond cleavage/C-N3 bond formation pathway.

Keywords: CC cleavage; azidation; azides; cyclobutanols; manganese.