Highly Z-selective metathesis homocoupling of terminal olefins.
Mo and W MonoAryloxide-Pyrrolide (MAP) olefin metathesis catalysts can couple terminal olefins to give as high as >98% Z-products in moderate to high yields with as little as 0.2% catalyst. Results are reported for 1-hexene, 1-octene, allylbenzene, allyltrimethylsilane, methyl-10-undecenoate, methyl-9-decenoate, allylB(pinacolate), allylOBenzyl, allylNHTosyl, and allylNHPh. It is proposed that high Z-selectivity is achieved because a large aryloxide only allows metallacyclobutanes to form that contain adjacent cis substituents and because isomerization of Z-product to E-product can be slow in that same steric environment.
Jiang
Annie J
AJ
Department of Chemistry 6-331, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Zhao
Yu
Y
Schrock
Richard R
RR
Hoveyda
Amir H
AH
D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis
D000475:Alkenes