title: Olefination of α,α'-divinyl ketones through catalytic Meyer-Schuster rearrangement.
abstract: The direct olefination of 1,4-dien-3-ones remains a synthetic challenge. A two-step protocol, employing acetylide addition followed by catalytic Meyer-Schuster rearrangement has been developed for the olefination of 1,4-pentadien-3-ones to afford [3]dendralenes. Many of the traditional methods for the Meyer-Schuster rearrangement of alkynyl carbinols are not suitable with these highly unsaturated substrates because of their acid sensitivity. Unexpected reactivity during attempted rearrangement, including Nazarov-type electrocyclizations, is presented, along with conditions to promote the Meyer-Schuster rearrangement of ethoxyacetylene adducts using catalytic VO(acac)(2).
authors.affiliation: Department of Chemistry, University of Alberta, E3-43 Gunning-Lemieux Chemistry Centre, Edmonton, AB T6G 2G2, Canada.
authors.forename: Curtis J
authors.initials: CJ
authors.lastname: Rieder
authors.forename: Karl J
authors.initials: KJ
authors.lastname: Winberg
authors.forename: F G
authors.initials: FG
authors.lastname: West
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry*; D002070:Butadienes / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D006046:Gold / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry*; D007662:Ketosis; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D002070:Butadienes; D007659:Ketones; D006046:Gold; C031763:1,3-butadiene