N-Methylpyrrolidone Hydroperoxide/Cs2 CO3 as an Excellent Reagent System for the Hydroxy-Directed Diastereoselective Epoxidation of Electron-Deficient Olefins

Napoleon John Victor; Janardhanan Gana; Kannoth Manheri Muraleedharan

doi:10.1002/chem.201501929

N-Methylpyrrolidone Hydroperoxide/Cs2 CO3 as an Excellent Reagent System for the Hydroxy-Directed Diastereoselective Epoxidation of Electron-Deficient Olefins

Chemistry. 2015 Oct 12;21(42):14742-7. doi: 10.1002/chem.201501929. Epub 2015 Aug 27.

Authors

Napoleon John Victor¹, Janardhanan Gana¹, Kannoth Manheri Muraleedharan²

Affiliations

¹ Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, India, Fax: (+91)-44 2257 4202.
² Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, India, Fax: (+91)-44 2257 4202. mkm@iitm.ac.in.

PMID: 26311172
DOI: 10.1002/chem.201501929

Abstract

This report introduces N-methylpyrrolidone hydroperoxide (NMPOOH)/base as an excellent reagent system for hydroxy-directed syn selective epoxidation of electron-deficient olefins, characterized by high diastereoselectivity, short reaction times and remarkable chemoselectivity, especially in presence of oxidatively labile nitrogen or sulfur atoms. NMPOOH also proves efficient in the oxidation of electron-deficient aromatic aldehydes, in the removal of oxazolidinone chiral auxiliary, and in the functionalization of alkenes and alkynes, showing wide application potential.

Keywords: chemoselectivity; diastereoselectivity; epoxidation; oxidation; peroxides.