First synthesis of optically pure selenuranes and stereoselective alkaline hydrolysis. Their application to asymmetric [2,3] sigmatropic rearrangement of allylic selenoxides

✍ Scribed by Noriyuki Kurose; Tamiko Takahashi; Toru Koizumi

• Book ID: 104207885
• Publisher: Elsevier Science
• Year: 1997
• Tongue: French
• Weight: 740 KB
• Volume: 53
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(97)00546-2

✦ Synopsis

The first synthesis of optically pure selenuranes 1 has been accomplished by utilizing 2exo-hydroxy-10-bomyl group as a chiral ligand. Complete retention of the configuration has been observed in alkaline hytl'olysis of 1 to give selenoxides 2. The structure of 1 and2 has been fully established by X-ray crystallography. [2,3] Sigmatropic rearrangement ofallylic selenoxides2 gavethe corresponding allylie alcohols 3 with up to 88% enantiomeric excess (ee). The [2,3] sigmatropic rearrangement of allylic selenoxides 2 progresses predominantly via an endo transition state.