title: Stereoselective access to Z and E macrocycles by ruthenium-catalyzed Z-selective ring-closing metathesis and ethenolysis.
abstract: The first report of Z-selective macrocyclizations using a ruthenium-based metathesis catalyst is described. The selectivity for Z macrocycles is consistently high for a diverse set of substrates with a variety of functional groups and ring sizes. The same catalyst was also employed for the Z-selective ethenolysis of a mixture of E and Z macrocycles, providing the pure E isomer. Notably, an ethylene pressure of only 1 atm was required. These methodologies were successfully applied to the construction of several olfactory macrocycles as well as the formal total synthesis of the cytotoxic alkaloid motuporamine C.
authors.affiliation: Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
authors.forename: Vanessa M
authors.initials: VM
authors.lastname: Marx
authors.forename: Myles B
authors.initials: MB
authors.lastname: Herbert
authors.forename: Benjamin K
authors.initials: BK
authors.lastname: Keitz
authors.forename: Robert H
authors.initials: RH
authors.lastname: Grubbs
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D047028:Macrocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D047028:Macrocyclic Compounds; D009942:Organometallic Compounds; D012428:Ruthenium