First Asymmetric Hetero Diels−Alder Reaction of 1-Sulfinyl Dienes with Nitroso Derivatives. A New Entry to the Synthesis of Optically Pure 1,4-Imino-l-ribitol Derivatives

• DOI: 10.1021/ol0063611
• Publication Date: 2002-07-26T06:06:54Z
• Authors: C. Arribas; M. Carmen Carreño; José L. García-Ruano; Justo F. Rodríguez; Mercedes Santos; M. Ascensión Sanz...
• Keywords: Magnetic Resonance Spectroscopy; Glycoside Hydrolases; Cyclization; Molecular Conformation; Indicators and Reagents; Stereoisomerism; Enzyme Inhibitors; 01 natural sciences; Ribitol; Nitroso Compounds; 0104 chemical sciences

Hetero Diels-Alder (HDA) cycloaddition of chiral 1-p-tolylsulfinyl-1,3-pentadiene with benzyl nitrosoformate, under mild conditions, yields 2H-1,2-oxazine 3 with complete regioselectivity and pi-facial diastereoselectivity. Sequential osmylation and protection of the resulting glycol gives the oxazine 5 which is directly transformed into enantiomerically pure 1,4,5-trideoxy-1,4-imino-L-ribitol 8 by reduction under Pd/C.