14 分子内光閉環反応を利用したロンジピネンの合成研究

概要

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α-Longipinene (1) is a sesquiterpene isolated from the essential oil of Pinus silvestris or Swedish sulfate turpentine, and the skeletone involves a pinane moiety. In this study the unique skeleton was constructed by intramolecular photocyclo-addition of cyclodecadiene derivatives as the key step. Trimethylcyclodecadienone (9) was synthesized from acetoxy-octalone (13) as shown in the text. Contrary to expectation, irradiation of (9) afforded only a Norish fission product (25) as the sole isolable product. On the other hand, triene (10) derived from (9) gave the desired photocyclized product (12) on sensitized photolysis. Norketone (11) was obtained from the latter and submitted to Tiffneau-Demyanov rearrangement giving ketone (31). Treatment of (31) with methyllithium followed by dehydration gave α-(1) and β-longipinenes (33).
天然有機化合物討論会の論文
1972-10-01