| Title: | "Z-Selective Cross-Metathesis and Homodimerization of 3E-1,3-Dienes: Reaction Optimization, Computational Analysis, and Synthetic Applications" |
| Author(s): | Luo SX; Cannon JS; Taylor BLH; Engle KM; Houk KN; Grubbs RH; |
| Address: | "Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology , Pasadena, California 91125, United States. Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States" |
| ISSN/ISBN: | 1520-5126 (Electronic) 0002-7863 (Linking) |
| Abstract: | "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" |
| Notes: | "PubMed-not-MEDLINELuo, Shao-Xiong Cannon, Jeffrey S Taylor, Buck L H Engle, Keary M Houk, K N Grubbs, Robert H eng 2016/10/18 J Am Chem Soc. 2016 Oct 26; 138(42):14039-14046. doi: 10.1021/jacs.6b08387. Epub 2016 Oct 17" |
