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

نویسندگان

  • Graham E. Dobereiner
  • Gulin Erdogan
  • Casey R. Larsen
  • Douglas B. Grotjahn
  • Richard R. Schrock
چکیده

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 Cn trans internal olefins into C2n−2 cis olefins and ethylene. This reaction is made possible with Ru-based “alkene zipper” 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− N)(MeCN)]X (X− = [B(3,5-(CF3)2C6H3)4] −, PF6 −, B(C6F5)4 −) isomerization catalysts.

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تاریخ انتشار 2014