Z-Selective Olefin Metathesis Processes Catalyzed by a Molybdenum Hexaisopropylterphenoxide Monopyrrolide Complex
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Schrock_Z-selective olefin.pdf
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Author(s)
Flook, Margaret M.
Jiang, Annie J.
Hoveyda, Amir H.
Schrock, Richard Royce
Muller, Peter
Date Issued
May 2009
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Flook, Margaret M., Annie J. Jiang, Richard R. Schrock, Peter Muller, and Amir H. Hoveyda. “Z-Selective Olefin Metathesis Processes Catalyzed by a Molybdenum Hexaisopropylterphenoxide Monopyrrolide Complex.” Journal of the American Chemical Society 131, no. 23 (June 17, 2009): 7962-7963.
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Author's final manuscript
Abstract
The molybdenum-based monoaryloxide monopyrrolide (MAP) species, Mo(NAd)(CHCMe[subscript 2]Ph)(C[subscript 4]H[subscript 4]N)(HIPTO) (2a), which contains “small” imido (Ad = 1-adamantyl) and “large” aryloxide (HIPTO = O-2,6(2,4,6-i-Pr[subscript 3]C[subscript 6]H[subscript 2])C[subscript 6]H[subscript 3]) ligands, catalyzes Z-selective metathesis reactions as a consequence of intermediate metallacyclobutane species not being able to have an (anti) substituent pointing toward the HIPTO group. Ring-opening metathesis polymerization (ROMP) of dicarbomethoxynorbornadiene (DCMNBD) with 2% 2a in toluene leads to >99% cis and >99% syndiotactic poly(DCMNBD), while ROMP of cyclooctene and 1,5-cyclooctadiene (300 equiv) with initiator 2a leads to poly(cyclooctene) and poly(cyclooctadiene) that have cis contents of >99%; all are previously unknown microstructures. Z-Selectivity is also observed in the metathesis of cis-4-octene and cis-3-hexene by initiator 2a to give cis-3-heptene.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ja902738u
