Rearrangement approaches to cyclic skeletons. IV The total synthesis of (.+-.)-pinguisone and (.+-.)-deoxopinguisone based on photochemical (1,3) acyl migration of a bicyclo(3.2.2)non-6-en-2-one.

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概要

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• The total synthesis of (±)-Pinguisone (<B>2</B>) and (±)-deoxopinguisone (<B>3</B>), [5–6] fused-ring sesquiterpenes, has been achieved starting from 1-methoxy-3,4,5-trimethylbenzene. 1-Methoxy-4,5,<I>endo</I>-8-trimethylbicyclo[2.2.2]non-5-en-2-one (<B>9</B>) was prepared selectively via facial selective Diels–Alder reaction of the diene derived from the benzene and 2-chloroacrylonitrile. Ring enlargement of <B>9</B> using (CH<SUB>3</SUB>)<SUB>3</SUB>SiCHN<SUB>2</SUB> and BF<SUB>3</SUB> etherate gave the corresponding bicyclo[3.2.2]oct-6-en-2-one (<B>8</B>). The photochemical [1,3] acyl migration of <B>8</B> gave the [5–6] fused-ring compound (<B>7</B>). The fourth methyl was introduced selectively by the conjugate addition of (CH<SUB>3</SUB>)<SUB>2</SUB>CuLi to the spiro[bicyclo[4.3.0]non-8-ene-3,2′-[1,3]dioxolan]-7-one prepared from <B>7</B>. Each furan ring of <B>2</B> and <B>3</B> was constructed via the corresponding butenolide derived from the γ-keto acid by acid-catalyzed dehydration.

• 公益社団法人 日本化学会の論文

著者

• Uyehara Tadao

  Department Of Applied Chemistry Faculty Of Engineering Utsunomiya University

• Kabasawa Yasuhiro

  Department Of Sport And Medical Science Faculty Of Physical Education Kokushikan University

• Kato Tadahiro

  Department of Applied Microbial Technology, Kumamoto Institute of Technology

関連論文

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