Mechanochemical Activation of Zinc and Application to Negishi Cross‐Coupling

Abstract

A form independent activation of zinc, concomitant generation of organozinc species and engagement in a Negishi cross‐coupling reaction via mechanochemical methods is reported. The reported method exhibits a broad substrate scope for both C(sp3)–C(sp2) and C(sp2)–C(sp2) couplings and is tolerant to many important functional groups. The method may offer broad reaching opportunities for the in situ generation organometallic compounds from base metals and their concomitant engagement in synthetic reactions via mechanochemical methods.

Palladium-catalyzed solid-state borylation of aryl halides using mechanochemistry

“…Notably, the strong mechanical agitation provided by ball milling enables efficient solid-state organic transformations. Thus far, mechanochemical palladiumcatalyzed cross-coupling reactions such as Suzuki-Miyaura [34][35][36][37][38][39][40][41][42][43][44][45][46][47], Buchwald-Hartwig [48][49][50][51][52], Sonogashira [53][54][55][56], Negishi [57], Mizoroki-Heck [58][59][60], and C-S bond-forming [61] reactions have been developed. Our group has also been interested in this class of mechanochemical transformations, particularly in the development of cross-coupling reactions that proceed in the solid state [43][44][45][46][47][48][49][50].…”

Vom inerten zum katalytisch aktiven Mahlmedium: Galvanostatische Beschichtung für direkte Mechanokatalyse

“…[1] Üblicherweise werden die chemischen Verbindungen durch Stoß-oder Scherkräfte zur Reaktion gebracht, die durch den Zusammenstoß von Mahlkugeln in vibrierenden oder rotierenden Mahlbechern ausgelöst werden. Mechanochemie hat sich für die Synthese kleiner organischer Moleküle, [1,2] Polymeren, [3] supramolekularer Strukturen, [4] funktionellen Materialien, [5] Nanopartikel, [6] organometallischer Verbindungen, [7] Arzneimittel, [8] und Biomoleküle [9] bewährt. Neben der Übertragung von Energie und dem Mischen von Reagenzien ist die Interaktion des Mahlkörpers mit dem Reaktionsgemisch im Allgemeinen unerwünscht.…”

Mechanochemical Asymmetric Cross‐Dehydrogenative Coupling Reaction: Liquid‐Assisted Grinding Enables Reaction Acceleration and Enantioselectivity Control

“…All these elegant findings intrigue us to preconceive that the participation of LAGs in metal‐catalyzed asymmetric reactions might lead to highly active chiral metal complexes through non‐covalent bond interaction and provide efficient control of both reactivity and enantioselectivity (Scheme , d). While there are previous examples where the chemo‐selectivity, rate, kinetics or products of a reaction have been changed, LAGs enabled enantio‐control is, to the best of our knowledge, unprecedented.…”