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Published October 26, 2016 | Supplemental Material
Journal Article Open

Z-Selective Cross-Metathesis and Homodimerization of 3E-1,3-Dienes: Reaction Optimization, Computational Analysis, and Synthetic Applications


Olefin metathesis reactions with 3E-1,3-dienes using Z-selective cyclometalated ruthenium benzylidene catalysts are described. In particular, a procedure for employing 3E-1,3-dienes in Z-selective homodimerization and cross-metathesis with terminal alkenes is detailed. The reaction takes advantage of the pronounced chemoselectivity of a recently reported ruthenium-based catalyst containing a cyclometalated NHC ligand for terminal alkenes in the presence of internal E-alkenes. A wide array of commonly encountered functional groups can be tolerated, and only a small excess (1.5 equiv) of the diene coupling partner is required to achieve high yields of the desired internal E,Z-diene cross-metathesis product. Computational studies have been performed to elucidate the reaction mechanism. The computations are consistent with a diene-first pathway. The reaction can be used to quickly assemble structurally complex targets. The power of this cross-metathesis reaction is demonstrated by the concise syntheses of two insect pheromones.

Additional Information

© 2016 American Chemical Society. Received: August 11, 2016. Publication Date (Web): September 30, 2016. We thank Dr. Scott C. Virgil and the Center for Catalysis and Chemical Synthesis (3CS) at Caltech and Kai Chen (Arnold Lab, Caltech) for assistance with preparative HPLC. The research described in this manuscript was supported financially by the ONR (Award Number N00014-12-1-0596) and the NIH (R01GM031332; F32GM103002, postdoctoral fellowship to J.S.C.; F32GM106596, postdoctoral fellowship to B.L.H.T.; F32GM108145, postdoctoral fellowship to K.M.E.). Materia, Inc. is thanked for the generous donation of catalysts 1–5. Calculations were performed on supercomputers from the DoD HPCMP Open Research Systems and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the NSF. The authors declare no competing financial interest.

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