Intramolecular cyclization of nerol and the related attack of (Z)-allylic alcohol moiety on the terminal olefin linkage as induced by TiCl4-PhNHMe complex. Synthesis of nezukone.

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概要

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• Nerol was cyclized to terpinyl chloride or bromide in the presence of TiX<SUB>4</SUB>–PhNHMe (1 : 1) complex (I, X= Cl, Br) in dichloromethane at −23 °C, geraniol being converted into geranyl halide by simple halogenation. Terminally modified derivatives YCH<SUB>2</SUB>C(Me)=CHCH<SUB>2</SUB>CH<SUB>2</SUB>CMe=CHCH<SUB>2</SUB>OH (Y=SiMe<SUB>3</SUB>, SnBu<SUB>3</SUB>) of (2<I>Z</I>,6<I>E</I>) configuration were cyclized by treatment with I to afford limonene in high yields and 100% selectivity. Cyclization of (2<I>Z</I>) isomers of CH<SUB>2</SUB>=CR–CH<SUB>2</SUB>CH<SUB>2</SUB>CMe=CHCH<SUB>2</SUB>OH (R=H, Me, Cl) produced seven-membered carbocyclic products in fair yields. The novel procedure has been utilized in the synthesis of nezukone from (2<I>E</I>)-3-isopropyl-2,6-heptadien-1-ol involving five steps.

• 公益社団法人 日本化学会の論文

著者

• SAITO Tadashi

  Department of Oral Surgery, Gunma University School of Medicine

• Oshima Koichiro

  Department Of Industrial Chemistry Faculty Of Engineering Kyoto University

• Nozaki Hitosi

  Department of Industrial Chemistry, Faculty of Engineering Kyoto University

• Itoh Akira

  Department of Applied Chemistry, Faculty of Engineering, Osaka University

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