Metal-assisted terpenoid synthesis. V. The catalytic trimerization of isoprene to trans-.BETA.-farnesene and its synthetic applications for terpenoids.
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概要
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Isoprene oligomerization was effected with a catalyst system Ni(OR)(η<SUP>3</SUP>-C<SUB>3</SUB>H<SUB>5</SUB>)PPh(NEt<SUB>2</SUB>)<SUB>2</SUB> (R=<I>n</I>-C<SUB>11</SUB>H<SUB>23</SUB>, <I>n</I>-C<SUB>15</SUB>H<SUB>31</SUB>) to give a linear trimer fraction above 70% yield. The major component of the trimer fraction is (<I>E</I>)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene (<I>trans</I>-β-farnesene) (<B>1</B>). The minor constituents of the fraction are (<I>E</I>)-2,6-dimethyl-10-methylene-1,6,11-dodecatriene. As slightly higher boiling point fractions, two cyclic trimers 1,5,9-trimethyl-1,5,9-cyclododecatriene and 1,5,10-trimethyl-1,5,9-cyclododecatriene were detected. Factors that influence the reaction path leading to <B>1</B> were discussed. Sesqui- and diterpenoids, including farnesyl acetate, farnesylacetone and isophytol were synthesised starting from <B>1</B>. A regioselective tail to tail coupling of <B>1</B> was achieved with a palladium catalyst to give the dimer C<SUB>30</SUB>H<SUB>48</SUB> which, upon catalytic hydrogenation, gave perhydrosqualene in 85% yield.
- 公益社団法人 日本化学会の論文
著者
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Otsuka Sei
Department of Chemistry, Faculty of Engineering Science, and Department of Polymer Science, Faculty of Science, Osaka University
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Akutagawa Susumu
Central Research Laboratory, Takasago Perfumery Co.
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Someya Taichi
Central Research Laboratory of Takasago Perfumery Co., Ltd.
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Takayama Kiyoshi
Central Research Laboratory, Takasago Perfumery Co. Ltd.
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Taketomi Takanao
Central Research Laboratory, Takasago Perfumery Co. Ltd.
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Kumobayashi Hidenori
Central Research Laboratory, Takasago Perfumery Co. Ltd.
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Akutagawa Susumu
Central Research Laboratory, Takasago Perfumery Co. Ltd.
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