Mild Decarboxylative C−H Alkylation: Computational Insights for Solvent‐Robust Ruthenium(II) Domino Manifold

Abstract

Computational studies on decarboxylative C-H alkenylations provided key insights into the solvent-robust nature of C-H activation/decarboxylation domino reactions. These properties were exploited for ruthenium(II)-catalyzed C-H alkylations by a decarboxylative process with ample scope under copper-free and silver-free reaction conditions.

Electrooxidative Ruthenium‐Catalyzed C−H/O−H Annulation by Weak O‐Coordination

“…Ther obust ruthenium(II) carboxylate manifold was fully tolerant of air and H 2 O, with optimal results obtained in as olvent mixture of tert-amyl alcohol and H 2 Ow ith sodium pivalate as the additive (entries [5][6][7][8][9][10]. Control experiments reflected the outstanding performance of the ruthenium(II) carboxylates [11] (entries [8][9][10][11][12][13][14][15][16][17][18][19], while typical iridium, cobalt, and palladium catalysts fell short in delivering the desired product 3aa (entries [11][12][13][14][15]. …”

Ruthenium(II)biscarboxylate‐Catalyzed Hydrogen‐Isotope Exchange by Alkene C−H Activation

“…During our mechanistic studies on kinetics of ruthenium‐catalyzed C−H activation, we observed the incorporation of deuterium into alkenes with unique selectivity features . Our investigations indicated that this profile was due to an unprecedented alkene deuteration, unexpectedly occurring prior to the C−H activation event.…”

“…The practical utility and key mechanistic implications of the C−H activation‐based HIE was next applied to the position‐ and chemo‐selective preparation of biorelevant, naturally occurring compounds. Hence, our HIE approach proved applicable towards the preparation of phthalides of type [D] 3 ‐ 5 b (Scheme a) – key structural motifs in various natural products – from substrate [D 2 ]‐ 4 without notable primary kinetic isotope effect (KIE) in the ruthenium oxidase, catalysis manifold (Scheme b).…”

Jenseits von Friedel und Crafts: dirigierte Alkylierung von C‐H‐Bindungen in Arenen

“…[75a] Es wurde gezeigt, dass die elektronischen Eigenschaften der Ausgangsbenzoesäuren das Ergebnis der Reaktion nur geringfügig beeinflussten und dass meta-substituierte Benzoesäuren überwiegend in der am wenigsten gehinderten Position alkyliert wurden. [76] Kurz darauf folgten Berichte über eine rhodium-/ kupfercokatalysierte,c arboxydirigierte ortho-Alkylierung mit konjugierten Ketonen, die in situ durch Dehydrierung der entsprechenden Ketone erzeugt wurden, [75b] sowie über eine rutheniumkatalysierte Oxidation/Alkylierung mit Allylalkoholen.…”