Gold(I)‐Catalyzed Protodecarboxylation of (Hetero)Aromatic Carboxylic Acids

Abstract

Golden delivery: A gold(I)-NHC complex catalyses the protodecarboxylation of various (hetero)aromatic acids. This methodology is simple, highly efficient and combines both the advantages of copper and silver methods with applications to completely deactivated substrates. Moreover, intermediates in this reaction have been isolated and fully characterized and provide fundamental insights into the mechanism of protodecarboxylation with gold.

Rhodium‐Catalyzed Annelation of Benzoic Acids with α,β‐Unsaturated Ketones with Cleavage of C−H, CO−OH, and C−C Bonds

“…[1] Initially, this approach was often limited by the use of complex directing groups, [2] which needed to be installed and later removed, thus adding steps to the overall process.Instate-ofthe-art methods,t he selectivity can be enforced even by ubiquitous functionalities,i ncluding ketone, [3] hydroxy, [4] or carboxylate groups. [6] Inspired by pioneering work by Miura and co-workers, [7] ah uge variety of carboxylatedirected sp 2 CÀH ortho-functionalizations have been developed for example,b yt he groups of Yu, [8] Li, [9] Daugulis, [10] Larrosa, [11] Ackermann, [12] Su, [13] Baidya, [14] our group, [15] and others. [6] Inspired by pioneering work by Miura and co-workers, [7] ah uge variety of carboxylatedirected sp 2 CÀH ortho-functionalizations have been developed for example,b yt he groups of Yu, [8] Li, [9] Daugulis, [10] Larrosa, [11] Ackermann, [12] Su, [13] Baidya, [14] our group, [15] and others.…”

“…[5] Thek ey advantages of carboxylate directing groups are their broad availability and the fact that they can be removed tracelessly or used as anchor points for further regiospecific CÀCo rC Àheteroatom bond-forming reactions through decarboxylative coupling. [6] Inspired by pioneering work by Miura and co-workers, [7] ah uge variety of carboxylatedirected sp 2 CÀH ortho-functionalizations have been developed for example,b yt he groups of Yu, [8] Li, [9] Daugulis, [10] Larrosa, [11] Ackermann, [12] Su, [13] Baidya, [14] our group, [15] and others. [16] Thep redominant pathways for ortho-CÀHf unctionalizations of carboxylates with a,b-unsaturated carbonyl compounds are oxidative Heck-type couplings (Scheme 1a), which lead either to ortho-vinylated carboxylates or to alkyl or alkenyl lactones.…”

Rhodium‐katalysierte Anellierung von Benzoesäuren mit α,β‐ungesättigten Ketonen durch C‐H‐, CO‐OH‐ und C‐C‐ Bindungsspaltung

“…[1] Anfangs wurden diese Reaktionen jedoch oftmals durch komplexe dirigierende Gruppen limitiert, [2] deren Einführung und spätere Entfernung die Atomçkonomie beeinträchtigen. [6] Aufbauend auf Pionierarbeiten von Miura, [7] wurde eine Vielzahl carboxylatdirigierter sp 2 C-H-ortho-Funktionalisierungen von Yu, [8] Li, [9] Daugulis, [10] Larrosa, [11] Ackermann, [12] Su, [13] Baidya, [14] unserer Gruppe [15] und anderen [16] entwickelt. [5] Entscheidende Vorteile von Carbonsäuren als dirigierende Gruppe sind eine breite Verfügbarkeit und die Mçglichkeit der Protodecarboxylierung oder weiterer ipso-Funktionalisierungen in Form von regiospezifischen C-C-oder C-Heteroatom-Bindungsknüpfungend urch decarboxylierende Kupplungen.…”

“…[5] Entscheidende Vorteile von Carbonsäuren als dirigierende Gruppe sind eine breite Verfügbarkeit und die Mçglichkeit der Protodecarboxylierung oder weiterer ipso-Funktionalisierungen in Form von regiospezifischen C-C-oder C-Heteroatom-Bindungsknüpfungend urch decarboxylierende Kupplungen. [6] Aufbauend auf Pionierarbeiten von Miura, [7] wurde eine Vielzahl carboxylatdirigierter sp 2 C-H-ortho-Funktionalisierungen von Yu, [8] Li, [9] Daugulis, [10] Larrosa, [11] Ackermann, [12] Su, [13] Baidya, [14] unserer Gruppe [15] und anderen [16] entwickelt.…”

Microwave-Assisted Silver-Catalyzed Protodecarboxylation and Decarboxylative Iodination of Aromatic Carboxylic Acids

“…Protodecarboxylation reaction is of high preparative utility in this field, first as a precursor step of decarboxylative cross-coupling reaction and also as a constructive model method for further functionalization design [8][9][10]. The traditional copper-catalyzed decarboxylation is hampered by the extremely high temperature and costly ligands [11].…”