title: Pd- and Rh-Catalyzed Hydroarylation of γ-(2-Methoxycarbonylphenyl)propargylic Alcohols: Approaches to 4- or 5-Substituted Seven-Membered Benzolactones and 3,3-Disubstituted Phthalides.
abstract: A study of the palladium-catalyzed hydroarylation/hydrovinylation reaction of γ-(2-methoxycarbonylphenyl)propargylic alcohols with aryl iodides/vinyl triflates and of the rhodium-catalyzed one with organoboron derivatives is described. The opposite regiochemical outcome of the two processes allows an easy selective approach to 5- or 4-substituted benzoxepin-1(3H)-ones by combining the hydroarylative/hydrovinylative step with cyclocondensation between -OH and -COOMe groups in the intermediate γ,γ-disubstituted or β,γ-disubstituted allylic alcohols. A one-flask procedure to give benzo[c]oxepin-1(3H)-ones directly from the starting alkyne has been also developed. Treatment of crude γ,γ-disubstituted allylic alcohols with NaOH, followed by acidification, affords 3,3-disubstituted phthalides.
authors.affiliation: †Dipartimento di Scienze Fisiche e Chimiche, Università di L'Aquila, Via Vetoio - 67010 Coppito (AQ), Italy.
authors.forename: Antonio
authors.initials: A
authors.lastname: Arcadi
authors.affiliation: ‡Dipartimento di Chimica e Tecnologie del Farmaco, Sapienza, Università di Roma, P.le A. Moro 5, 00185, Rome, Italy.
authors.forename: Giancarlo
authors.initials: G
authors.lastname: Fabrizi
authors.affiliation: ‡Dipartimento di Chimica e Tecnologie del Farmaco, Sapienza, Università di Roma, P.le A. Moro 5, 00185, Rome, Italy.
authors.forename: Antonella
authors.initials: A
authors.lastname: Goggiamani
authors.affiliation: †Dipartimento di Scienze Fisiche e Chimiche, Università di L'Aquila, Via Vetoio - 67010 Coppito (AQ), Italy.
authors.forename: Fabio
authors.initials: F
authors.lastname: Marinelli
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D001572:Benzofurans / Q000737:chemistry*; D002384:Catalysis; D007783:Lactones / Q000737:chemistry*; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry; D020005:Propanols / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry
chemical_list: D000480:Alkynes; D001572:Benzofurans; D007783:Lactones; D020005:Propanols; C006463:allyl alcohol; D010165:Palladium; C082022:phthalide; D012238:Rhodium