Remote functionalization of hydrocarbons with reversibility enhanced stereocontrol

Alexandre Vasseur (1) , Lionel Perrin (2) , Odile Eisenstein (3) , Ilan Marek (1)

1 Technion - Israel Institute of Technology [Haifa]
2 ITEMM - Interface Theory Experiment : Mechanism & Modeling
3 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

Remote functionalization of hydrocarbons could be achieved through successive zirconocene-mediated allylic C–H bond activations followed by a selective C–C bond cleavage. Determination of the reaction mechanism by density functional theory (DFT) calculations shows that the high stereocontrol observed in this process results from a large number of energetically accessible equilibria feeding a preferred reactive channel that leads to the major product. A distinctive consequence of this pattern is that stereoselectivity is enhanced upon heating.

Domaines: Chimie théorique et/ou physique; Catalyse

Alexandre Vasseur, Lionel Perrin, Odile Eisenstein, Ilan Marek. Remote functionalization of hydrocarbons with reversibility enhanced stereocontrol. Chemical Science, 2015, 6 (5), pp.2770-2776. ⟨10.1039/C5SC00445D⟩. ⟨hal-01152129⟩