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, affordi...

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Published in:Synthesis (Stuttgart) 2017-05, Vol.49 (9), p.1972-1982
Main Authors: Carosso, Serena, Memeo, Misal Giuseppe, Bovio, Bruna, Valletta, Elena, Macchi, Beatrice, Quadrelli, Paolo
Format: Article
Language:English
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Summary: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.
ISSN:0039-7881
1437-210X
DOI:10.1055/s-0036-1588695