Probing the mechanism of the Petasis olefination reaction by atmospheric pressure chemical ionization mass and tandem mass spectrometry

Eduardo Cesar Meurer; Leonardo Silva Santos; Ronaldo Aloise Pilli; Marcos N Eberlin

doi:10.1021/ol027439b

Probing the mechanism of the Petasis olefination reaction by atmospheric pressure chemical ionization mass and tandem mass spectrometry

Org Lett. 2003 May 1;5(9):1391-4. doi: 10.1021/ol027439b.

Authors

Eduardo Cesar Meurer¹, Leonardo Silva Santos, Ronaldo Aloise Pilli, Marcos N Eberlin

Affiliation

¹ Institute of Chemistry, State University of Campinas-UNICAMP, 13083-970 Campinas, SP, Brazil.

PMID: 12713281
DOI: 10.1021/ol027439b

Abstract

Atmospheric pressure chemical ionization mass (APCI-MS) and tandem mass spectrometry (APCI-MS/MS) is used to probe the mechanism of the Petasis olefination reaction. Oxatitanacycle intermediates 4 were transferred from solution to the gas phase, detected as 4H+ by APCI-MS with characteristic Ti-isotopic patterns, and structurally characterized by APCI-MS/MS. Detection of 4H+, which upon collision activation dissociates to both 3H+ and Cp(2)TiOH+, fully supports the Hughes mechanism as depicted above. [reaction: see text]