Direct synthesis of 6-oxabicyclo[3.2.1]octane derivatives from deoxyinososes

✍ Scribed by Regine Blattner; Robert J. Ferrier

• Book ID: 102991092
• Publisher: Elsevier Science
• Year: 1986
• Tongue: English
• Weight: 812 KB
• Volume: 150
• Category: Article
• ISSN: 0008-6215
• DOI: 10.1016/0008-6215(86)80012-x

✦ Synopsis

In the presence of bases, even those (for example, pyridine) normally used for acylation reactions, 2L-(2,4,5/3)-2,3,4-tibenzoyloxy-5-hydroxycyclohexanone (3) readily gives 2r_-(2,4/3)-2,3,4-tribenzoyloxycyclohex-5-enone or aromatic products. Under acid conditions, efficient 0-acylation and tetrahydropyranylation can be effected. The main product (60% isolated) formed on treatment of 3 with diazomethane is (lR,2S,3R,4S,5S)-2,3,4-tribenzoyloxy-l-hydroxy-6-oxabicyclo [3.2.l]octane (l5); small proportions of the epimeric Spiro-epoxides and 1-acetyl-6 benzoyloxy-7-methoxy-lH-indazole are also formed. On photobromination, the acetate ( 17) of I5 undergoes substitution at C-7 and, from the product, C-formyldeoxyinositol derivatives are produced. *Dedicated to Professor N. K. Kochetkov. +Functionalised Carbocycles from Carbohydrates, Part 9. For Part 8, see ref. Il.