Nickel/Zinc Chloride-Promoted Domino Reaction of polyenynes

镍/氯化锌促进的多烯多米诺反应

• 批准号: 16590010
• 负责人: IKEDA Shin-ichi
• 金额: $ 2.24万
• 依托单位: Nagoya City University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16590010/
• 关键词: nickel; zinc chloride; enone; dienyne; domino process

A Ni(0)/ZnCl_2 system effectively promotes the coupling of enones and alkene-tethered alkynes. In the reaction with 1,6-enynes, the oxidative cyclization of Ni(0) species on enones across the alkyne part followed by ZnCl_2-promoted cleavage generates alkenylnickel intermediates. Subsequent migratory insertion of the tethered alkene occurs with 5-exo-cyclization. When the resulting alkylnickel intermediates have β-hydrogen atoms, the reaction terminates by β-hydrogen elimination to provide cyclopentane derivatives. On the other hand, an alkylnickel intermediate that does not have β-hydrogen atoms undergoes the insertion of a second alkene unit to cause a domino effect via a three-fold C-C bond formation process.

Ni(0)/ZnCl_2体系有效促进了烯酮和烯烃束缚的炔烃的偶联。在与 1,6-烯炔的反应中，Ni(0) 物质在烯酮上穿过炔烃部分发生氧化环化，随后 ZnCl_2 促进裂解生成烯基镍中间体。随后通过 5-外环化发生束缚烯烃的迁移插入。当所得烷基镍中间体具有β-氢原子时，反应通过β-氢消除而终止，得到环戊烷衍生物。另一方面，不具有β-氢原子的烷基镍中间体会插入第二个烯烃单元，通过三重C-C键形成过程引起多米诺骨牌效应。

项目成果

Ni-Catalyzed, ZnCl2-Assisted Domino Coupling of Enones, Alkynes, and Alkenes.

Ni 催化、ZnCl2 辅助的烯酮、炔烃和烯烃的多米诺偶联。

• DOI: 10.1002/chin.200451036
• 发表时间: 2004
• 期刊: ChemInform
• 作者: Shin‐ichi Ikeda;Reiko Sanuki;H. Miyachi;Hitoshi Miyashita;M. Taniguchi;K. Odashima
• 通讯作者: K. Odashima

Modern Organonickel Chemistry, Chapter 4.Reaction with Alkynes

现代有机镍化学，第 4 章：与炔烃的反应

• 发表时间: 2005
• 作者: H.Takahashi;H.Mitsuzuka;K.Nishiyama;S.Ikegami;Y.Hari;Shin-ichi Ikeda
• 通讯作者: Shin-ichi Ikeda