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Ylide-Functionalized Phosphines: Strong Donor Ligands for Homogeneous Catalysis.

ABSTRACT: Phosphines are important ligands in homogenous catalysis and have been crucial for many advances, such as in cross-coupling, hydrofunctionalization, or hydrogenation reactions. Herein we report the synthesis and application of a novel class of phosphines bearing ylide substituents. These phosphines are easily accessible via different synthetic routes from commercially available starting materials. Owing to the extra donation from the ylide group to the phosphorus center the ligands are unusually electron-rich and can thus function as strong electron donors. The donor capacity surpasses that of commonly used phosphines and carbenes and can easily be tuned by changing the substitution pattern at the ylidic carbon atom. The huge potential of ylide-functionalized phosphines in catalysis is demonstrated by their use in gold catalysis. Excellent performance at low catalyst loadings under mild reaction conditions is thus seen in different types of transformations.

SUBMITTER: Scherpf T

PROVIDER: S-EPMC6174943 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Ylide-Substituted Phosphines with a Cyclic Ylide-Backbone: Angle Dependence of the Donor Strength.

Project description:Ylide-substituted phosphines (YPhos) have been shown to be highly electron-rich and efficient ligands in a variety of palladium catalyzed transformations. Here, the synthesis and characterization of novel YPhos ligands containing a cyclic backbone architecture are reported. The ligands are easily synthesized from a cyclic phosphonium salt and the chlorophosphines Cy2PCl (L1) and Cy(FluMe)PCl (L2, with FluMe = 9-methylfluorenyl) and were characterized in both solution and solid states. The smaller PCy2-substituted ligand, L1, readily formed the biscoordinate L1 2 Pd species when treated with Pd2(dba)3 and showed no activity in palladium-catalyzed amination reactions even when applied as defined palladium(II) η3-allyl, t-Bu-indenyl, or cinnamyl precursors. Bulkier fluorenyl-substituted ligand L2 similarly was inactive, despite its ability to form the stable monophosphine complex L2·Pd(dba). Assessment of the electronic properties by experimental and computational methods revealed that L1 and L2 are considerably less electron-rich than previously synthesized YPhos ligands. This was shown to be the result of the small P-C-S bond angle, which is sterically enforced due to the cyclic nature of the backbone. Density functional theory calculations revealed that the small angle results in an increased s-character of the lone pair at the ylidic carbon atom and leads to a polarization of the C-P bond toward the carbon atom, thus decreasing the electron density at the phosphorus atom. The results demonstrate the tunability of the donor strength of YPhos ligands by modification of the ligand backbone beyond simple changes of the substitution pattern and are thus important for future ligand design, with a careful balance of many factors to be considered to achieve catalytic activity.

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Towards the rational design of ylide-substituted phosphines for gold(i)-catalysis: from inactive to ppm-level catalysis.

Project description:The implementation of gold catalysis into large-scale processes suffers from the fact that most reactions still require high catalyst loadings to achieve efficient catalysis thus making upscaling impractical. Here, we report systematic studies on the impact of the substituent in the backbone of ylide-substituted phosphines (YPhos) on the catalytic activity in the hydroamination of alkynes, which allowed us to increase the catalyst performance by orders of magnitude. While electronic changes of the ligand properties by introduction of aryl groups with electron-withdrawing or electron-donating groups had surprisingly little impact on the activity of the gold complexes, the use of bulky aryl groups with ortho-substituents led to a remarkable boost in the catalyst activity. However, this catalyst improvement is not a result of an increased steric demand of the ligand towards the metal center, but due to steric protection of the reactive ylidic carbon centre in the ligand backbone. The gold complex of the thus designed mesityl-substituted YPhos ligand YMesPCy2, which is readily accessible in one step from a simple phosphonium salt, exhibited a high catalyst stability and allowed for turnover numbers up to 20 000 in the hydroamination of a series of different alkynes and amines. Furthermore, the catalyst was also active in more challenging reactions including enyne cyclisation and the formation of 1,2-dihydroquinolines.

| S-EPMC8179644 | biostudies-literature

<b>Selective Pd-Catalyzed Monoarylation of Small Primary Alkyl Amines through Backbone-Modification in Ylide-Functionalized Phosphines (YPhos)</b>.

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Project description:Comprehensive mechanistic insights into the activity of different catalysts based on different ligands are important for further ligand design and catalyst improvement. Herein, we report a combined computational and experimental study on the mechanism and catalytic activity of the ylide-substituted phosphine Cy3P-C(Me)PCy2 (keYPhos, L1) in C-N coupling reactions including a comparison with the established and often-applied phosphines CyJohnPhos (L2) and P(tBu)3 (L3). Density functional theory (DFT) calculations together with the possible isolation of several intermediates within the catalytic cycle demonstrate that L1 readily forms low-coordinated palladium complexes [such as L1·Pd(dba)], which easily undergo oxidative addition and subsequent amine coordination as well as reductive elimination. Due to the possible opening and closing of the P-C-P angle in L1, the steric bulk can be adjusted to the metal environment so that L1 retains its conformation throughout the whole catalytic cycle, thus leading to fast catalysis at room temperature. Comparative studies of the three ligands with Pd2dba3 as a Pd source show that only L1 efficiently allows for the coupling of aryl chlorides at room temperature. DFT studies suggest that this is mainly due to the reluctance/inability of L2 and L3 to form the catalytically active species under these reaction conditions. In contrast, the YPhos ligand readily forms the prereactive complex and undergoes the first oxidative addition reaction. These observations are confirmed by kinetic studies, which indicate a short induction period for the formation of the catalytically active species of L1, followed by fast catalysis. This behavior of L1 is due to its unique electronic and steric properties, which support low activation barriers and fast catalyst generation.

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| S-EPMC4210111 | biostudies-literature

Palladium Complexes Based on Ylide-Functionalized Phosphines (YPhos): Broadly Applicable High-Performance Precatalysts for the Amination of Aryl Halides at Room Temperature.

Project description:Palladium allyl, cinnamyl, and indenyl complexes with the ylide-substituted phosphines Cy3 P+ -C- (R)PCy2 (with R=Me (L1) or Ph (L2)) and Cy3 P+ -C- (Me)PtBu2 (L3) were prepared and applied as defined precatalysts in C-N coupling reactions. The complexes are highly active in the amination of 4-chlorotoluene with a series of different amines. Higher yields were observed with the precatalysts in comparison to the in situ generated catalysts. Changes in the ligand structures allowed for improved selectivities by shutting down β-hydride elimination or diarylation reactions. Particularly, the complexes based on L2 (joYPhos) revealed to be universal precatalysts for various amines and aryl halides. Full conversions to the desired products are reached mostly within 1 h reaction time at room temperature, thus making L2 to one of the most efficient ligands in C-N coupling reactions. The applicability of the catalysts was demonstrated for aryl chlorides, bromides and iodides together with primary and secondary aryl and alkyl amines, including gram-scale applications also with low catalyst loadings of down to 0.05 mol %. Kinetic studies further demonstrated the outstanding activity of the precatalysts with TOF over 10.000 h-1 .

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Uncovering Subtle Ligand Effects of Phosphines Using Gold(I) Catalysis.

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