Stereoselective Synthesis of 4,5-Diethylidene-Oxazolidinones as New Dienes in Diels-Alder Reactions

✍ Scribed by Rafael Martínez; Hugo A. Jiménez-Vázquez; Alicia Reyes; Joaquín Tamariz

• Publisher: John Wiley and Sons
• Year: 2002
• Tongue: German
• Weight: 339 KB
• Volume: 85
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/1522-2675(200202)85:2<464::aid-hlca464>3.0.co;2-u

✦ Synopsis

The N-substituted isomeric (4Z,5Z)-and (4E,5Z)-4,5-diethylideneoxazolidin-2-ones 5 and 6 were synthesized, the latter being favored during the one-step process from the a-diketone 1c and different isocyanates. The steric interaction between the N-substituent and the Me group attached to the exocyclic diene moiety plays a decisive role in controlling the observed stereoselectivity, as suggested by the calculated free energies of the two isomers. Both dienes undergo efficient additions to symmetric dienophiles in thermal Diels-Alder reactions to yield the adducts 11 and 13, respectively. These molecules displayed interesting CÀH ¥¥¥ p, and CÀH ¥¥¥ X (X O, Cl) interactions according to their X-ray crystal structures. Isomers 6 suffered highly stereo-and regioselective additions with nonsymmetrical dienophiles such as methyl vinyl ketone or methyl propiolate. Steric interactions, promoted by the inward-pointing Me group in 6, seem to explain such selectivity. These results have also been rationalized by ab initio calculations in terms of the FMO theory.