N,O-Nucleosides from Ene Reaction of (Nitrosocarbonyl)mesitylene with Crotyl Alcohol: Selectivity, Scope, and Limitations

Abstract

The (nitrosocarbonyl)mesitylene intermediate undergoes an ene reaction with crotyl alcohol, affording two regioisomeric adducts in fair yields. The sterically demanding (nitrosocarbonyl)mesitylene slightly shifts the C2/Markovnikov orientation towards a C3/anti-Markovnikov­ pathway, affording a 5-hydroxyisoxazolidine that serves as a synthon for the preparation of N,O-nucleoside analogues through the Vorbrüggen protocol. The selectivity of the ene reaction is discussed in the light of C=C bond polarization and steric effects. The structures of the N,O-nucleosides are assigned and discussed on the basis of spectroscopic observations and X-ray analysis.

Key words

N,O-nucleosides - ene reaction - nitroso carbonyls - crotyl alcohol - Vorbrüggen protocol

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