A One-Pot Tandem Olefin Isomerization/Metathesis-Coupling (ISOMET) Reaction

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• 作者：Graham E. Dobereiner ; Gulin Erdogan ; Casey R. Larsen ; Douglas B. Grotjahn ; Richard R. Schrock
• 刊名：ACS Catalysis
• 出版年：2014
• 出版时间：September 5, 2014
• 年：2014
• 卷：4
• 期：9
• 页码：3069-3076
• 全文大小：341K
• ISSN：2155-5435

文摘

A tandem catalytic reaction has been developed as part of a process to discover tungsten-based olefin metathesis catalysts that have a strong preference for terminal olefins over cis or trans internal isomers in olefin metathesis. This tandem isomerization/terminal olefin metathesis reaction (ISOMET) converts C_n trans internal olefins into C_2n鈥? cis olefins and ethylene. This reaction is made possible with Ru-based 鈥渁lkene zipper鈥?catalysts, which selectively isomerize trans olefins to an equilibrium mixture of trans and terminal olefins, plus tungsten-based metathesis catalysts that react relatively selectively with terminal olefins to give Z homocoupled products. The most effective catalysts are W(NAr)(C₃H₆)(pyr)(OHIPT) (Ar = 2,6-diisopropylphenyl; pyr = pyrrolide; OHIPT = O-2,6-(2,4,6-i-Pr₃C₆H₂)₂C₆H₃) and various [CpRu(P鈥揘)(MeCN)]X (X鈥?/sup> = [B(3,5-(CF₃)₂C₆H₃)₄]鈥?/sup>, PF₆鈥?/sup>, B(C₆F₅)₄鈥?/sup>) isomerization catalysts.

Keywords:

tandem catalysis; olefin; metathesis; isomerization; ruthenium; tungsten