Reaction of Tetrahydropyranyl Ethers with Triethylsilyl Trifluoromethanesulfonate–2,4,6-Collidine Combination: Speculation on the Intermediate, Efficient Deprotection, and Application to Efficient Ring-Closing Metathesis as a Tether

✍ Scribed by Hiromichi Fujioka; Takashi Okitsu; Takuya Ohnaka; Yoshinari Sawama; Ozora Kubo; Kazuhisa Okamoto; Yasuyuki Kita

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 207 KB
• Volume: 349
• Category: Article
• ISSN: 1615-4150
• DOI: 10.1002/adsc.200600572

✦ Synopsis

Abstract

The reaction of tetrahydropyranyl (THP) ethers with triethylsilyl trifluoromethanesulfonate (TESOTf)–2,4,6‐collidine proceeded via collidinium salt intermediates to give the alcohol and 4‐triethylsiloxybutanal in good yields. The structure of the intermediate was confirmed by ^1^H NMR and FAB‐MS studies and by trapping it with EtOH. The reaction was applied for mild, efficient, and highly chemoselective deprotection method of THP ethers. The characteristic feature of the reaction is that the reaction conditions are weakly basic. Then, the reaction can proceed without affecting acid‐labile protecting groups. Furthermore, the intermediates from alkenol–THP ether were trapped with other alkenols to give acyclic mixed acetals, which were subjected to efficient ring‐closing metathesis by using the tetrahydropyranyl unit as a tether.