title: Synthesis of Linear (Z)-α,β-Unsaturated Esters by Catalytic Cross-Metathesis. The Influence of Acetonitrile.
abstract: Kinetically controlled catalytic cross-metathesis reactions that generate (Z)-α,β-unsaturated esters selectively are disclosed. A key finding is that the presence of acetonitrile obviates the need for using excess amounts of a more valuable terminal alkene substrates. On the basis of X-ray structure and spectroscopic investigations a rationale for the positive impact of acetonitrile is provided. Transformations leading to various E,Z-dienoates are highly Z-selective as well. Utility is highlighted by application to stereoselective synthesis of the C1-C12 fragment of biologically active natural product (-)-laulimalide.
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467, USA.
authors.forename: Elsie C
authors.initials: EC
authors.lastname: Yu
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467, USA.
authors.forename: Brett M
authors.initials: BM
authors.lastname: Johnson
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA.
authors.forename: Erik M
authors.initials: EM
authors.lastname: Townsend
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA.
authors.forename: Richard R
authors.initials: RR
authors.lastname: Schrock
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467, USA. amir.hoveyda@bc.edu.
authors.forename: Amir H
authors.initials: AH
authors.lastname: Hoveyda
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000138:chemical synthesis* / Q000737:chemistry; D007700:Kinetics; D018942:Macrolides / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure
chemical_list: D000097:Acetonitriles; D004952:Esters; D018942:Macrolides; C117305:laulimalide; C032159:acetonitrile
keywords: alkenes; catalysis; cross-metathesis; enoates; molybdenum