Catalytic Suzuki Coupling Reactions by Amido Phosphine Complexes of Palladium

Abstract

Treatment of PdCl2(PhCN)2 with [NP]Li(THF)2 ([NP]- = N-(2-(diphenylphosphino)phenyl)-2,6-diisopropylanilide) in THF affords dimeric {[NP]PdCl}2, which reacts with tricyclohexylphosphine to produce [NP]PdCl(PCy3). The two phosphorus donors in [NP]PdCl(PCy3) are mutually cis, as indicated by the solution NMR and X-ray crystallographic studies. Both {[NP]PdCl}2 and [NP]PdCl(PCy3) are highly active catalyst precursors for Suzuki coupling reactions of a wide array of aryl halides, including those featuring electronically deactivated and sterically hindered characteristics.

Insights into Sonogashira Cross‐Coupling by High‐Throughput Kinetics and Descriptor Modeling

“…The Hammett s À parameter [76,77] is an excellent descriptor in this case. Note, however, that the literature contains diverse reports: Similar correlations were reported for Suzuki, [78][79][80] Heck, [81][82][83][84][85] and carbonylation reactions [86] even though different Hammett parameters were used: Milstein and Herrmann reported that s À p parameters yielded the best fits, whereas other studies applied s p parameters. Even a s þ p correlation to establish a stabilization of a positive charge in the transition state was reported.…”

An Efficient Class of P,N‐Type “PhMezole‐phos” Ligands: Applications in Palladium‐Catalyzed Suzuki Coupling of Aryl Chlorides

“…To evaluate the effectiveness of the hemilabile ligands, sterically hindered 2-chloro-m-xylene was used as the benchmark substrate (Table 1). For commonly used organic solvents [tetrahydrofuran (THF), dioxane, N,N-dimethylformamide (DMF), toluene, mesitylene and tBuOH], dioxane was the best single solvent (Table 1, Entries 1 and [8][9][10][11][12]. K 3 PO 4 ·H 2 O was found to be the best base in this catalytic system.…”

Three types of reactions with intramolecular five-membered ring compounds in organic synthesis

“…(42-1) and Table 3 [173][174][175][176]. Especially, phosphite palladacycles 42-2 shows the highest TON, 10 8 [174,175].…”

“…Especially, phosphite palladacycles 42-2 shows the highest TON, 10 8 [174,175]. N-(2-(Diphenylphosphino)phenyl)-2,6-diidopropylanilinde palladacycles 42-3 do not have a metal-carbon bond, but, they also show high catalytic activities [176].…”

“…(43-1) [178]. Table 3 Reaction conditions and catalyst studies on the Suzuki coupling of p-halobenzene derivaitives and phenylboric acid [173][174][175][176][177] Catalyst (mol%) …”