Catalytic Version of Enediyne Cobalt‐Mediated Cycloaddition and Selective Access to Unusual Bicyclic Trienes

Abstract

Go cyclic! The use of [Co(H)(PMe3)4] as a cobalt catalyst allows the previously unattainable catalytic version of the cobalt-mediated cycloaddition of enediynes without the requirement of thermal or light activation (see scheme). The importance of a chelating group on the substrate that can selectively direct the reaction pathway toward the classical polycyclic 1,3-cyclohexadienes or a new family of bicyclic trienes is also demonstrated.

A HELIXOL‐Derived Bisphosphinite Ligand: Synthesis and Application in Gold‐Catalyzed Enynes Cycloisomerization

“…We thus turned our attention towards low‐valent cobalt catalyst HCo(PMe 3 ) 4 . Indeed, in 2013, we disclosed the first use of HCo(PMe 3 ) 4 in triynes and enediynes cycloaddition reaction . Of particular interest was the ability of this catalyst to react at low loading and without external activation.…”

Société Chimique de France 2014 Prize Winners

“…Malacria’s research interests include transition‐metal‐catalyzed cyclization and cycloisomerization reactions, radical chemistry, and asymmetric synthesis involving heteroatoms. He has reported in Chemistry—A European Journal on catalytic cobalt‐mediated enediyne cycloaddition reactions,1a and in Angewandte Chemie on the synthesis of triangular tripalladium cations 1b. Malacria is on the International Advisory Board of Chemistry—An Asian Journal and was closely associated with the European Journal of Organic Chemistry firstly as Co‐Editor (2002) and subsequently Editorial Board member (2003–2012) and Chairman (2005–2012).…”

Preise der Société Chimique de France 2014

“…Sein Interesse gilt übergangsmetallkatalysierten Cyclisierungen und Cycloisomerisierungen, der Radikalchemie und der asymmetrischen Synthese unter Beteiligung von Heteroatomen. In Chemistry—A European Journal hat er katalytische cobaltvermittelte Endiincycloadditionen vorgestellt1a und in der Angewandten Chemie die Synthese von kationischen Palladium‐Dreiecksclustern 1b. Malacria gehört dem International Advisory Board von Chemistry—An Asian Journal an und war mit dem European Journal of Organic Chemistry als Co‐Editor (2002), Mitglied des Editorial Board (2003–2012) und dessen Vorsitzender (2005–2012) eng verbunden.…”