From Stable PH-Ylides to α-Carbanionic Phosphines as Ligands for Zwitterionic Catalysts.

Although ylides are commonly used reagents in organic synthesis, the parent methylphosphine MePH2 only exists in its phosphine form in the condensed phase. Its ylide tautomer H3 P+ -CH2 - is considerably higher in energy. Here, we report on the formation of bis(sulfonyl)methyl-substituted phosphines of the type (RO2 S)2 C(H)-PR2, which form stable PH ylides under ambient conditions, amongst the first examples of an acyclic phosphine which only exists in its PH ylide form. Depending on the exact substitution pattern the phosphines form an equilibrium between the PH ylide and the phosphine form or exist as one of both extremes. These phosphines were found to be ideal starting systems for the facile formation of α-carbanionic phosphines. The carbanion-functionalization leads to a switch from electron-poor to highly electron-rich phosphines with strong donor abilities and high basicities. Thus, the phosphines readily react with different electrophiles exclusively at the phosphorus atom and not at the carbanionic center. Furthermore, the anionic nature of the phosphines allows the formation of zwitterionic complexes as demonstrated by the isolation of a gold(I) complex with a cationic metal center. The cationic gold center allows for catalytic activity in the hydroamination of alkyne without requiring a further activation step.

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

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.

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

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.