title: Propargyltrimethylsilanes as allene equivalents in transition metal-catalyzed [5 + 2] cycloadditions.
abstract: Conventional allenes have not been effective π-reactive 2-carbon components in many intermolecular cycloadditions including metal-catalyzed [5 + 2] cycloadditions. We report herein that rhodium-catalyzed [5 + 2] cycloadditions of propargyltrimethylsilanes and vinylcyclopropanes provide, after in situ protodesilylation, a highly efficient route to formal allene cycloadducts. Propargyltrimethylsilanes function as safe, easily handled synthetic equivalents of gaseous allenes and hard-to-access monosubstituted allenes. In this one-flask procedure, they provide cycloadducts of what is formally addition to the more sterically encumbered allene double bond.
authors.affiliation: Department of Chemistry, Department of Chemical and Systems Biology, Stanford University , Stanford, California 94305-5080, United States.
authors.forename: Paul A
authors.initials: PA
authors.lastname: Wender
authors.forename: Fuyuhiko
authors.initials: F
authors.lastname: Inagaki
authors.forename: Magnus
authors.initials: M
authors.lastname: Pfaffenbach
authors.forename: Matthew C
authors.initials: MC
authors.lastname: Stevens
mesh_terms: D000466:Alkadienes / Q000737:chemistry*; D002384:Catalysis; D061565:Cycloaddition Reaction; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D028561:Transition Elements / Q000737:chemistry*; D014297:Trimethylsilyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D000466:Alkadienes; D028561:Transition Elements; D014297:Trimethylsilyl Compounds; C025947:propadiene; D012238:Rhodium