A general approach to the stereoselective synthesis of spiroketals. A total synthesis of the pheromones of the olive fruit fly and related compounds

• Published in: Journal of the American Chemical Society Vol. 110; no. 6; pp. 1901 - 1910
• Main Authors: DeShong, Philip, Waltermire, Robert E, Ammon, Herman L
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 01.03.1988; Amer Chemical Soc
• Subjects: Biochemistry. Physiology. Immunology; Biological and medical sciences; Chemistry; Chemistry, Multidisciplinary; Dacus oleae; Exact sciences and technology; Fundamental and applied biological sciences. Psychology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Insecta; Invertebrates; Organic chemistry; Physical Sciences; Physiology. Development; Preparations and properties; Science & Technology; Tephritidae; Intramolecular reaction; Five membered ring; Diol; Insecta; Pheromone; Acid catalysis; Oxygen heterocycle; Spiran; Stereoselectivity; Acetal; Cyclization; Arthropoda; Six membered ring; Oxidation; Invertebrata; Diptera
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja00214a039

A general, highly stereoselective approach to the synthesis of spiroketal systems of the 1,7-dioxaspiro[5.5]undecane and 1,6-dioxaspiro[4.5]decane families is discussed. The key reaction in the approach features oxidation of a suitably substituted furfurol derivative 1 to afford pyranone 2, which subsequently undergoes stereoselective intramolecular ketalization under acidic conditions to furnish spiroketal 3, carrying the 2,6-anti relationship. Analogous methodology is employed to synthesize in a stereoselective fashion model systems for the avermectin spiroketal moieties 9-11 and the pheromones of the olive fruit fly (39 and 40).