title: Validating the alkene and alkyne hydrophosphonylation as an entry to organophosphonates.
abstract: The first paper on the hydrophosphonylation of terminal alkenes was published in 1958 by Stiles and coworkers. Afterwards various papers described organometal-catalyzed and free-radical reactions leading to linear anti-Markovnikov adducts and/or branched Markovnikov products. In 1996 Han and Tanaka reported the first example of alkyne hydrophosphonylation catalyzed by a palladium complex. Further studies using other metal catalysts registered poor selectivity as mixtures of adducts were obtained in most of the cases examined. The first example of alkyne hydrophosphonylation by H-phosphonates under free-radical conditions leading to Z- and E-vinylphosphonates in a 1 : 1 ratio was reported by our group. Nevertheless, Z- to E-isomerization took place upon irradiation in the presence of a thiol.
authors.affiliation: Interdisciplinary Center for the Study of Inflammation, Università di Ferrara, Via L. Borsari 46, 44121 Ferrara, Italy. adn@unife.it.
authors.forename: Alessandro
authors.initials: A
authors.lastname: Dondoni
authors.forename: Alberto
authors.initials: A
authors.lastname: Marra
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D015394:Molecular Structure; D063065:Organophosphonates / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D000475:Alkenes; D000480:Alkynes; D063065:Organophosphonates