Synthesis 2017; 49(09): 1972-1982
DOI: 10.1055/s-0036-1588695
paper
© Georg Thieme Verlag Stuttgart · New York

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

Serena Carosso
a   Department of Chemistry, University of Pavia, Viale Taramelli 12, 27100 Pavia, Italy   Email: paolo.quadrelli@unipv.it
,
Misal Giuseppe Memeo
a   Department of Chemistry, University of Pavia, Viale Taramelli 12, 27100 Pavia, Italy   Email: paolo.quadrelli@unipv.it
,
Bruna Bovio
a   Department of Chemistry, University of Pavia, Viale Taramelli 12, 27100 Pavia, Italy   Email: paolo.quadrelli@unipv.it
,
Elena Valletta
b   Department of System Medicine, University of Rome Tor Vergata, Via Montpellier 1, 00133 Roma, Italy
,
Beatrice Macchi
a   Department of Chemistry, University of Pavia, Viale Taramelli 12, 27100 Pavia, Italy   Email: paolo.quadrelli@unipv.it
,
Paolo Quadrelli*
a   Department of Chemistry, University of Pavia, Viale Taramelli 12, 27100 Pavia, Italy   Email: paolo.quadrelli@unipv.it
› Author Affiliations
Further Information

Publication History

Received: 09 December 2016

Accepted after revision: 09 January 2017

Publication Date:
01 February 2017 (online)


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.

Supporting Information