Electron-transfer-catalyzed dimerization of trans-anethole: detection of the distonic tetramethylene radical cation intermediate by extractive electrospray ionization mass spectrometry

Cesar A Marquez; Haoyang Wang; Francesco Fabbretti; Jürgen O Metzger

doi:10.1021/ja806791c

Electron-transfer-catalyzed dimerization of trans-anethole: detection of the distonic tetramethylene radical cation intermediate by extractive electrospray ionization mass spectrometry

J Am Chem Soc. 2008 Dec 24;130(51):17208-9. doi: 10.1021/ja806791c.

Authors

Cesar A Marquez¹, Haoyang Wang, Francesco Fabbretti, Jürgen O Metzger

Affiliation

¹ Institut für Reine and Angewandte Chemie der Universität Oldenburg, P.O. Box 2503, 26111, Germany.

PMID: 19049280
DOI: 10.1021/ja806791c

Abstract

The desolvating droplets of EESI were used as microreactor for the mass spectrometric study of short-lived transients of reactions in condensed liquid phase in the millisecond time region. The electron-transfer-catalyzed dimerization of trans-anethole was investigated and the intermediates in the radical cation chain reaction were isolated and characterized by MS-MS. The distonic tetramethylene radical cation 3(o)(*+) was detected as intermediate, and its cyclization to give the cyclobutane radical cation 3(c)(*+) was observed giving strong evidence that the reaction takes place stepwise.