Enantioselective synthesis and absolute configuration of (−)-pulo'upone by asymmetric intramolecular diels-alder reaction

✍ Scribed by Wolfgang Oppolzer; Dominique Dupuis; Giovanni Poli; Tony M. Raynham; Gérald Bernardinelli

• Book ID: 104217658
• Publisher: Elsevier Science
• Year: 1988
• Tongue: French
• Weight: 297 KB
• Volume: 29
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)82216-9

✦ Synopsis

Pulo'upone (1) was synthesized via an asymmetric, bornane-10,2-sultam-directed, intramolecular Diels-Alderaction

(2 -+ 2) and a 2_pyridylcuprate/allylacetate coupling (18 + I). The (6'R, 9'S, 13'R. 14'R)configuration of (-)-I follows from an X-ray diffraction analysis of the cycloaddition product 2.

Pulo'upone, isolated in small quantity from the caphalaspidean mollusk Philinopsis speciosa, has been assigned structure 1. on the basis of spectral evidence 2). A very recent communication described a synthesis of racemic 1. 3).