Amidophosphine‐stabilized palladium complexes catalyse Suzuki–Miyaura cross‐couplings in aqueous media

Jansa, Josef; Řezníček, Tomáš; Dostál, Libor; Růžičková, Zdena; Bureš, Filip; Jambor, Roman

doi:10.1002/aoc.3539

Cited by 12 publications

(17 citation statements)

References 61 publications

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“…Both complexes share similar bond lengths and angles around the Pd center, i. e., Pd−Cl (2.2774 and 2.3089 Å); Pd−P (2.2989 and 2.3533 Å); and Pd−P−N (113.09 and 113.83°), for C1 and C2 , respectively. These are comparable to those previously reported by Jin [40] (Pd−Cl=2.2772 Å) and Jambor [41] (Pd−P=2.3124 Å and P−N=1.6901 Å).…”

Section: Entry Ligand Vco [Cm−1] Refsupporting

confidence: 91%

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Easily Prepared Mono(N,N‐dialkylamino)phosphine Palladium(II) Complexes: Structural and Catalytic Evaluation

et al. 2021

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The search for efficient, active and universal catalyst systems for transition-metal catalyzed cross-coupling reactions, continues to be of interest to researchers world-wide. Herein, we report two new Pd(II) complexes, effortlessly prepared from N,Ndialkylamino-phosphines for Suzuki-Miyaura cross-coupling reactions. These sufficiently hindered (% V Bur = 30.0-31.5 %) and electron rich (v CO = 1947.41-1946.29 cm À 1 ) aminophosphines formed active catalysts for Suzuki-Miyaura coupling of aryl bromides and chlorides. Palladium-catalyzed cross-coupling reactions are indispensable tools in synthesis, providing easy access to CÀ C and CÀ X (X=N, O, S, F, Si, and B) bonds. [1,2] Among them is the Suzuki-Miyaura reaction, widely used in pharmaceuticals, [3] agrochemicals, [4] natural products, [5] materials science [6] and process chemistry. [7] As the application of this versatile reaction broadens, the need for robust, highly active catalyst systems increases. Pioneering contributions in this regard have been trialkyl-, biaryl-, ferrocenyl-and adamantyl-based phosphines developed by Fu, [8] Buchwald, [9] Hartwig [10] and Beller, [11] respectively. Notable contributions have subsequently been made by Kwong, [12] Verkade, [13] Reetz, [14] Stradiotto, [15] Hong, [16] and many more.Our focus is on aminophosphines, [17,18] pioneered as ligands in Suzuki-Miyaura coupling by Woolins [19] and now applicable in other catalyst systems such as intermolecular hydroamination of alkenes, [20] alkylation of amines by alcohols, [21] and amination of aryl-substituted allylic alcohols. [22] This class of ligands allows for easy tuning of donor and steric capacities by varying substituents on the N-(abundance of amines, including easily accessible imidazol-2-ylidene-and pyridinylide amines), the Pcenter or both. [23][24][25][26][27][28][29] Arylamino groups attenuate the basicity of the P-donor atom through resonance and σ-electron withdrawal, while aliphatic amino groups increase the basicity due to the absence of the π-system. [30] This was idependently demonstrated by Ziółkowski [31] and Woollins, [32] studying the electronic properties of N-pyrrolyl-and N-pyrrolidinyl-phosphines employing v CO of trans-[RhCl(CO)L 2 ], respectively. Their studies also revealed the alkyl-based [P(NC 4 H 8 ) 3 ] (1951 cm À 1 ) as a better donor compared to its aromatic counterpart [P(NC 4 H 4 ) 3 ] (2012 cm À 1 ) (Table 1). Most notable was the finding that Pbasicity increases with decrease of amino-substituents, Ph 2 P-(NR 2 ) > PhP(NR 2 ) 2 > P(NR 2 ) 3 . This trend was further confirmed by Burrows and co-workers, [33] in their parameterization studies of N-carbazolyl phosphines which showed a decrease in donor character with increase in number of N-carbazolyl substituents in the order [PPh 2 (NC 12 H 8 )] < [PPh(NC 12 H 8 ) 2 ] < [P(NC 12 H 8 ) 3 ] (Table 1). Furthermore, Singh and co-workers identified [PPh (NEt 2 ) 2 )] as a poor donor than [PPh 2 (NEt 2 )], with electron descriptors of v CO = 2007 cm À 1 and 1974 cm À 1 , and 1 J PSe = 761 Hz an...

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Section: Entry Ligand Vco [Cm−1] Refsupporting

confidence: 91%

“…Similarly, the use of conventional solvents THF, DMF, and CH 2 Cl 2 gave poor yields (Table S3). With optimum conditions determined, [42][43][44] the catalytic efficacies of C1 and C2 were compared using electronically diverse aryl bromides and [40] (PdÀ Cl = 2.2772 Å) and Jambor [41] (PdÀ P = 2.3124 Å and PÀ N = 1.6901 Å).…”

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Easily Prepared Mono(N,N‐dialkylamino)phosphine Palladium(II) Complexes: Structural and Catalytic Evaluation

et al. 2021

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“…Over the past few decades, water-soluble catalysts have gained great interest for the development of novel catalysts for greener chemical processes and synthetic methods. − Water-soluble catalysts and ligands are widely utilized in organic reactions because of environmental and economical considerations …”

Section: Introductionmentioning

confidence: 99%

“…Although Suzuki coupling reactions are among the most useful methods for the synthesis of carbon skeletons, there are still improvements that could be made to render this technique even more effective. It has also been demonstrated that the use of palladium phosphine species ,, is an excellent strategy for Suzuki couplings under very low palladium loadings. However, phosphine ligands are expensive, toxic, and usually hydrophobic and air-sensitive; therefore, cross-coupling reactions under phosphine-free conditions are still an important challenge for researchers. − Recently, different phosphine-free ligands as diverse as N-heterocyclic carbenes, diimines, diamines, and amides have attracted considerable attention as competent ligands for Suzuki reactions.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Method for Suzuki Reactions in Aqueous Media

et al. 2018

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Herein, we report the crystal structure and characterization of mono-6-( l -aminopropanol)-deoxy-β-cyclodextrin (L n @β-CD). A highly efficient, in situ generated catalyst, PdCl 2 (L n @β-CD), was synthesized for palladium-catalyzed cross-coupling reactions under mild reaction conditions, and the use of this catalyst in Suzuki cross-couplings was investigated. Low palladium loadings of 0.01 mol % PdCl 2 (L n @β-CD) (Pd accounted for approximately 8.4% of the catalyst by mass) were found to be highly efficient for Suzuki cross-couplings in water and afforded the corresponding biaryl compounds in excellent yields. The catalyst can be recycled and reused.

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“…131～133 ℃; 1 H NMR (400 MHz, CDCl 3 ) δ: 8.30 (d, J＝8.7 Hz, 2H), 7.71 (d, J＝8.7 Hz, 2H), 7.56 (d,J＝ 8.4 Hz,2H),7.47 (d,J＝8.4 Hz,2H); HRMS (ESI) calcd for C 12 H 8 ClNNaO 2 [M＋Na] ＋ 256.0135, found 256.0110. 4-三氟甲基-4'-硝基联苯(3ag) [24] : 白色固体, 产率 93%. m.p.…”

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An Efficient Palladium Nanoparticles Catalytic System for Suzuki Coupling Reactions

Li¹,

Zhao²,

Liu³

et al. 2019

Chinese Journal of Organic Chemistry

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Amidophosphine‐stabilized palladium complexes catalyse Suzuki–Miyaura cross‐couplings in aqueous media

Cited by 12 publications

References 61 publications

Easily Prepared Mono(N,N‐dialkylamino)phosphine Palladium(II) Complexes: Structural and Catalytic Evaluation

Easily Prepared Mono(N,N‐dialkylamino)phosphine Palladium(II) Complexes: Structural and Catalytic Evaluation

Highly Efficient Method for Suzuki Reactions in Aqueous Media

An Efficient Palladium Nanoparticles Catalytic System for Suzuki Coupling Reactions

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