Rapid synthesis of arylgold compounds using dielectric heating

Abstract

Dielectric heating has been successfully used in the preparation of a range of arylgold compounds. The approach is tolerant of a number of functional groups and rapidly generates the organometallic complexes in moderate to excellent yields.

Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes

“…(JohnPhos)AuCl and ( t -BuXPhos)AuCl, were prepared by displacement of dimethyl sulfide from Me 2 SAuCl by JohnPhos or t -BuXPhos [23–24]. The (NHC)AuCl (NHC = SIMes, IMes, SIPr, IPr) [19,25] precursors as well as arylgold compounds 1 – 3 [14] were prepared following literature procedures. The arylboronic acids, alkynes, phenols, and Cs 2 CO 3 (powder) were obtained from Aldrich and used as received.…”

“…We recently reported the synthesis of arylgold compounds using a focused microwave reactor (Scheme 1) [14]. Although microwave-assisted reactions are legion in organic chemistry, they are rare in organometallic synthesis [15–21].…”

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

“…These conclusions lend additional understanding to the mechanism of previously studied organoboron-to-gold transmetalation reactions 20–24 according to the principle of microscopic reversibility, which dictates that if the organogold-to-boron transmetalation proceeds through a tetracoordinate boronate intermediate, the organoboron-to-gold transmetalation must also proceed through this type of intermediate.…”

“…The reverse transmetalation from organoboron to gold(I), in contrast, has been studied, especially stoichiometrically, wherein Gray has performed several founding studies. 20–24 Thus, knowledge of the favored position (thermodynamics) and accessibility (kinetics) of this reaction in both directions would be helpful for further reaction design. After our initial publication, Stephan and Hashmi disclosed a stoichiometric organogold-to-boron transmetlation reaction, 19 bolstering the range of systems for such transmetalation chemistry.…”

Fundamental Elementary Steps in Gold Chemistry

“…Further optimization of Scheme 3.51 Attempted β-hydride elimination from an (NHC)ethylgold(I) complex. Dipp = (2,6-diisopropyl)phenyl the reaction conditions employing microwave irradiation led to shorter reaction times [139]. A large variety of aryl and vinyl groups was shown to undergo the transmetallation with phosphine gold(I) halide complexes [126,138,[140][141][142][143].…”