Synthesis of highly oxygenated enantiomerically pure cis-bicyclo[4.3.0]nonanes from secondary sugar allyltin derivatives

✍ Scribed by Sławomir Jarosz; Katarzyna Szewczyk; Anna Zawisza

• Publisher: Elsevier Science
• Year: 2003
• Tongue: English
• Weight: 324 KB
• Volume: 14
• Category: Article
• ISSN: 0957-4166
• DOI: 10.1016/s0957-4166(03)00310-0

✦ Synopsis

Secondary sugar allyltin derivatives of the D-series: Sug-CH(SnBu 3 )-CH CH 2 (obtained in an S N 2% reaction of the corresponding primary allylic mesylates with 'Bu 3 SnCu') with the S-configuration at the stereogenic center bearing the -SnBu 3 group decompose at 140°C to dienoaldehydes: CH 2 CH-CH CH-[(CHOR) 3 ]-CHO with the cis geometry across the internal double bond. Such aldehydes react with the stabilized Wittig reagents to afford trienes, cyclization of which provides highly oxygenated enantiomerically pure cis-bicyclo [4.3.0]nonenes. This methodology is complementary to that recently proposed by us leading to such bicyclic systems, but with the trans junction between the five-and six-membered rings.