Double-Bond Isomerization: Highly Reactive Nickel Catalyst Applied in the Synthesis of the Pheromone (9Z,12Z)-Tetradeca-9,12-dienyl Acetate.
Double-Bond Isomerization: Highly Reactive Nickel Catalyst Applied in the Synthesis of the Pheromone (9Z,12Z)-Tetradeca-9,12-dienyl Acetate.
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DOI：
10.1021/acs.orglett.5b01230
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发表时间：
2015-05
期刊：
影响因子：
5.2
通讯作者：
F. Weber;Anastasia Schmidt;Philipp Roese;Michel Fischer;O. Burghaus;G. Hilt
中科院分区：
文献类型：
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作者：
F. Weber;Anastasia Schmidt;Philipp Roese;Michel Fischer;O. Burghaus;G. Hilt
以NiCl2(Dppp)或NiCl2(Dppe)为催化剂，配以锌粉、ZnI2和Ph2Ph组成的高活性镍催化剂用于端烯异构化合成Z-2-烯烃。2-烯烃的双键构型可以通过反应温度来控制，从而以优异的产率和高的Z-选择性生成2-Z-烯烃。在所提出的机理的基础上，通过1，2-氢化物从金属到Ph2P配体的转移，抑制了其他构型异构体的形成，如3-烯烃。然后将镍催化的异构化反应应用于含有2Z，5Z-二烯亚基的信息素(9Z，12Z)-十四-9，12-二烯基乙酸酯的合成。
A highly reactive nickel catalyst comprising NiCl2(dppp) or NiCl2(dppe) with zinc powder, ZnI2 and Ph2PH, was applied in the isomerization of terminal alkenes to Z-2-alkenes. The double-bond geometry of the 2-alkene can be controlled via the reaction temperature to yield the 2-Z-alkenes in excellent yields and high Z-selectivities. The formation of other constitutional isomers, such as 3-alkenes, is suppressed on the basis of the proposed mechanism via a 1,2-hydride shift from the metal to the Ph2P ligand. The nickel-catalyzed isomerization reaction was then applied in the synthesis of (9Z,12Z)-tetradeca-9,12-dienyl acetate, a pheromone with a 2Z,5Z-diene subunit.