A General Method for the Direct α‐Arylation of Aldehydes with Aryl Bromides and Chlorides

Biaryl Phosphane Ligands in Palladium‐Catalyzed Amination

“…[2] These phosphines have been used as ligands for gold, [3][4][5][6][7][8][9][10][11] silver, [12] rhodium, [13,14] ruthenium [15][16][17] and copper [18] where they have been shown to impart improvements in reactivity and catalyst stability. It is in reactions catalyzed by palladium, however, that they have had by far the greatest impact including the Sonogashira, [19] Negishi, [20] Hiyama, [21][22][23] Kumada [24] and Suzuki [25][26][27][28][29][30] cross-coupling reactions, Heck reaction, [31][32][33] enolate arylation [34][35][36][37] and allylation, [38] reductive cyclization [39] and etherification, [40][41][42][43] silylation, [44] borylation, [45][46][47] cyanation, [48,…”

An Improved Protocol for the Pd-Catalyzed α-Arylation of Aldehydes with Aryl Halides

“…Although we previously suggested that water content may be important in these α-arylation reactions,5 our early experiments did not completely establish its significance. We began our new investigation by studying the effects of water in our Pd(OAc) 2 /BINAP catalytic system.…”

“…In 2007, our research group reported a protocol for the α-arylation of aldehydes with both aryl bromides and aryl chlorides under mild reaction conditions 5. More recently, a similar α-arylation reaction has been described with aryl bromides and a limited set of activated aryl chlorides using dppf and QPhos as the ligands, respectively 6,7.…”

Complementary isonitrile-based multicomponent reactions for the synthesis of diversified cytotoxic hemiasterlin analogues

“…The syntheses relied on an allylpalladium-catalyzed α-arylation of isobutyraldehyde with an appropriate aryl or heteroaryl bromide, in the presence of catalytic Q-phos, 13 cleanly affording the desired aldehydes in yields up to 75%. Alternative palladium-catalyzed protocols, based on palladium diacetate as the catalyst, 14 or involving vinyl acetates as coupling components, 15 proved to be less effective.…”