Pyrazinium Salts as Efficient Organocatalysts of Mild Oxidations with Hydrogen Peroxide

• DOI: 10.1002/adsc.201000906
• Publication Date: 2011-04-13T01:49:32Z
• Authors: Petra Ménová; František Kafka; Hana Dvořáková; Smita Gunnoo; Miloslav Šanda; Radek Cibulka
• Keywords: 01 natural sciences; 0104 chemical sciences

AbstractA series of 3‐substituted pyrazinium tetrafluoroborates was prepared as simple analogues of flavinium salts which are efficient organocatalysts for oxidations with hydrogen peroxide. It was shown that pyrazinium derivatives with an electron‐withdrawing substituent catalyze mild oxidations of sulfides to sulfoxides and Baeyer–Villiger oxidations in a similar way to flavinium catalysts. The most reactive catalyst, 3‐cyanopyrazinium tetrafluoroborate, was efficiently employed in preparative sulfoxidations of aromatic and aliphatic sulfides as well as in Baeyer–Villiger oxidations of cyclobutanones. A proposed mechanism for the catalysis is based on the formation of pyrazine hydroperoxide which is the agent oxidizing the substrate.