|Budget Amount *help
¥2,100,000 (Direct Cost : ¥2,100,000)
Fiscal Year 1995 : ¥600,000 (Direct Cost : ¥600,000)
Fiscal Year 1994 : ¥1,500,000 (Direct Cost : ¥1,500,000)
1.In order to study oxidative transformation of 1-hydroxybicyclo [5.3.1] undec-2-enes into bicyclo [5.3.1] undec-1-en-2-ones, two types of starting materials, iodides and aldehydes, were prepared, that is, 5- (5-iodopentyl) cyclohex-2-en-1-one and 5- (3-oxo-4-cyclohexenyl) hexanal from 2-cyclohexenone, and 5- [2- (2-iodoethyl) benzyl] cyclohex-2-en-1-one and 2- [(3-oxo-4-cyclohexenyl) methyl] phenylethnal from 1,4-cyclohexadienone monoethylene acetal. However unfortunately, attempted intramolecular Barbier reaction of the above two iodides and cyclization reaction of the above two aldehydes with samarium iodide proved to be unsuccessful, and desired 1-hydroxybicyclo [5.3.1] undec-2-enes were scarcely obtainable. This is mostly because of great difficulty in eight membered ring formation by use of the above reaction conditions.
2.As part of utilization of (+) -nopinone toward enantioselective synthesis of natural products, chemical transformation of (+) -nopinone into (+) -apoverbenone and (+) -verbenone was examined. After all, the phenylsulfenylation-dehydrosulfenylation method was proved to be effective for this purpose, and (+) -apoverbenone and verbenone were prepared in high overall yields by use of this methodology.