The Role of Metal Hydroxide Complexes in Late Transition Metal‐Mediated Transmetalation Reaction: The Case of Gold

Abstract

In gold chemistry, the hydroxide function on the metal center was observed to act as a potent transmetalation group facilitator when reacted with boronic acids leading to the exceedingly rapid formation of gold-aryl bonds.

NMR spectroscopy studies of electronic effects and equilibrium in the organogold-to-boron transmetalation reaction and studies towards its application to the alkoxyboration addition of boron–oxygen σ bonds to alkynes

“…Aryl gold complex 6.1 was prepared from IPrAuCl according to a literature procedure 32 in 63% yield. 1 H NMR ( d 8- toluene, 400 MHz) ™ 7.27 (d, J = 6.5 Hz, 2H), 7.20 (t, J = 6.7 Hz, 2H), 7.09–7.05 (m, 4H), 6.73 (d, J = 6.6 Hz, 2H), 6.40 (s, 2H), 3.34 (s, 3H), 2.68 (br m, 4H), 1.46 (d, J = 5.5 Hz, 12 H), 1.11 (d, J = 5.6 Hz, 12 H).…”

Reaktivität von Goldkomplexen in metallorganischen Elementarreaktionen

“…Nolans Gruppe untersuchte die Reaktion von Arylboronsäuren mit AuCl(IPr) genauer. [103] Die Verwendung von Kaliumhydroxid anstelle von Cs 2 CO 3 ermçglichte die Tr ansmetallierung bei Raumtemperatur.E sw urde angenommen, dass die Bildung einer Gold(I)-Hydroxidspezies als Schlüsselintermediat auftritt (Schema 38), obgleich auch eine alternative Route mit Beteiligung eines Borats nicht ausgeschlossen wurde.…”

Fundamental Elementary Steps in Gold Chemistry

“…Nolan studied the reaction of arylboronic acids and [AuCl(IPr)] in more detail [144]. The synthetic protocol was improved by using potassium hydroxide as the base, allowing for the transmetallation to be performed at room temperature.…”