Palladium-Catalyzed Carbonylative Cross-Coupling Reaction of Arylboronic Acids with Aryl Electrophiles:  Synthesis of Biaryl Ketones

Abstract

The carbonylative cross-coupling reaction of arylboronic acids with aryl electrophiles (ArI, ArBr, and ArOTf) to yield unsymmetrical biaryl ketones was carried out in anisole at 80 °C in the presence of a palladium catalyst and a base. The reaction selectively proceeded under an atmospheric pressure of carbon monoxide when PdCl2(PPh3)2 (3 mol %)/K2CO3 (3 equiv) were used for aryl iodides and PdCl2(dppf) (3 mol %)/K2CO3 (3 equiv)/KI (3 equiv) for the bromides or the triflates. The carbonylation of arylboronic acids with benzyl halides gave aryl benzyl ketones.

Palladium nanoparticle-graphene hybrids as active catalysts for the Suzuki reaction

“…As an efficient catalyst in organic reactions, it can offer the most favorable combination of activity and selectivity [16]. One of the well-known reactions catalyzed by palladium is the Suzuki coupling reaction, which is a powerful and convenient synthetic method in organic chemistry to generate biaryls, conducting polymers, and liquid crystals [17][18][19][20][21].…”

Convergent Synthesis of Dronedarone, an Antiarrhythmic Agent

“…The residue was purified by flash column chromatography on silica gel eluting with CH 2 Cl 2 /MeOH=9 : 1 to give 7 (1.27 g, 46%) as a yellow amorphous solid. IR ν max : 2959, 1603, 1246 cm -3-(4-(3-(dibutylamino)propoxy)benzoyl)-benzofuran-5-yl)methanesulfonamide (Dronedarone, 2) According to the literature, 17) a mixture of 6 (0.149 g, 0.380 mmol), 7 (0.128 g, 0.420 mmol), PdCl 2 (PPh 3 ) 2 (8.0 mg, 0.0114 mmol), and K 2 CO 3 (0.158 g, 1.14 mmol) was filled with CO, and dry anisole (2.3 mL) was added. The mixture was vigorously stirred at 80°C for 23 h. After reaction was completed, the mixture was filtered through Celite.…”

“…Therefore, we considered that our methodology could be adapted for the synthesis of dronedarone (2) having a 2-alkylbenzo[b] furan core. Our synthetic plan is shown in Chart 3; biaryl ketone of 2 would be formed at the last stage by carbonylative SuzukiMiyaura cross-coupling 17) with 3-iodobenzo[b] furan 6 and arylboronic acid 7 aiming for a convergent process, and 6 would be derived from alkyne 8 by our developed iodocyclization protocol. Aryl alkyne 8 would be formed by Sonogashira coupling of corresponding iodoarene 9 and 1-hexyne.…”

Carbonylative Cross-Coupling Reaction of Ethynylstibane with Aryl Iodides

“…[14][15][16][17][18][19][20][21] The organoantimony(III) [Sb(III)] compounds are relatively stable and can be prepared easily compared to organoantimony(V) and hypervalent antimony compounds. The facile access of Sb(III) compounds stimulated us to employ them as practical organic reagents.…”

“…12,13) One useful application of these transmetallating agents is carbonylative cross-coupling reaction which leads to the formation of unsymmetrical ketones in one-pot operation from an appropriate transmetallating agent and organic halides under carbon monoxide (CO) atmosphere. [14][15][16][17][18][19][20][21] The organoantimony(III) [Sb(III)] compounds are relatively stable and can be prepared easily compared to organoantimony(V) and hypervalent antimony compounds. The facile access of Sb(III) compounds stimulated us to employ them as practical organic reagents.…”