Insertion of nitriles into zirconocene 1-aza-1,3-diene complexes: chemoselective synthesis of N-H and N-substituted pyrroles

Shasha Yu; Meijun Xiong; Xin Xie; Yuanhong Liu

doi:10.1002/anie.201407221

Insertion of nitriles into zirconocene 1-aza-1,3-diene complexes: chemoselective synthesis of N-H and N-substituted pyrroles

Angew Chem Int Ed Engl. 2014 Oct 20;53(43):11596-9. doi: 10.1002/anie.201407221. Epub 2014 Sep 9.

Authors

Shasha Yu¹, Meijun Xiong, Xin Xie, Yuanhong Liu

Affiliation

¹ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032 (P. R. China).

PMID: 25205544
DOI: 10.1002/anie.201407221

Abstract

The direct insertion of nitriles into zirconocene-1-aza-1,3-diene complexes provides an efficient, chemoselective, and controllable synthesis of N-H and N-substituted pyrroles upon acidic aqueous work-up. The outcome of the reaction (that is, the formation of N-H or N-substituted pyrroles) results from the different cyclization patterns, which depend on the relative stability and reactivity of the enamine-imine tautomers formed by hydrolysis of the diazazirconacycles.

Keywords: azazirconacycles; cyclization; insertion; nitriles; pyrroles.