title: Titanium and Zirconium Hydride-Catalyzed Regioselective Isomerization of 1,4-Dihydrofulvenes: Access to 1-Substituted 1,2-Dihydrofulvenes.
abstract: Zirconium hydride-catalyzed C═C double bond migration from nonconjugated to conjugated dienes is described. Applied to 1-substituted 1,4-dihydrofulvenes, the migration leads selectively to 1-substituted 1,2-dihydrofulvenes. The C═C double bond migration can also be catalyzed by titanium hydride, allowing a one-pot procedure to provide 1-substituted 1,2-dihydrofulvenes from pentafulvenes via two titanium-catalyzed steps. This sequence was proven to be temperature-dependent, allowing the selective access to a conjugated or nonconjugated adduct by a simple temperature tuning. The synthetic potential of the methodology was illustrated by the diastereoselective synthesis of a polyhydroxycyclopentane.
authors.affiliation: Institut de Chimie Moléculaire de Reims, CNRS (UMR 7312), Université de Reims , 51687 Cedex 2 Reims, France.
authors.forename: Jomy
authors.initials: J
authors.lastname: Joseph
authors.affiliation: National Institute for Interdisciplinary Science and Technology , CSIR-NIIST, Industrial Estate P.O., Trivandrum 19, Kerala, India.
authors.forename: Preethanuj
authors.initials: P
authors.lastname: Preethalayam
authors.affiliation: National Institute for Interdisciplinary Science and Technology , CSIR-NIIST, Industrial Estate P.O., Trivandrum 19, Kerala, India.
authors.forename: K V
authors.initials: KV
authors.lastname: Radhakrishnan
authors.affiliation: Institut de Chimie Moléculaire de Reims, CNRS (UMR 7312), Université de Reims , 51687 Cedex 2 Reims, France.
authors.forename: Florian
authors.initials: F
authors.lastname: Jaroschik
authors.affiliation: Institut de Chimie Moléculaire de Reims, CNRS (UMR 7312), Université de Reims , 51687 Cedex 2 Reims, France.
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Vasse