Synthesis and Application of 2,6‐Bis(trifluoromethyl)‐4‐pyridyl Phosphanes: The Most Electron‐Poor Aryl Phosphanes with Moderate Bulkiness

Highly Enantioselective Rhodium‐Catalyzed Addition of Arylboroxines to Simple Aryl Ketones: Efficient Synthesis of Escitalopram

“…Despite the recent advances in asymmetric additions of arylboron reagents to aldehydes, activated ketones, or ketones in an intramolecular fashion, few successful results were reported on asymmetric intermolecular addition of aryl boron reagents to simple ketones . Low enantioseletivities were reported for either chiral nickel or rhodium catalysts (a Ni/chiral N‐heterocyclic carbene ligand: 36 % ee , a Rh/chiral bisphosphine: 38 % ee , a Rh/chiral diene: 68 % ee ) . A low yield was also observed in our previous study, albeit with an improved enantioselectivity (25 % yield, 95 % ee ) .…”

Solid‐Supported Rhodium(0) Nano‐/Microparticles: An Efficient Ligand‐Free Heterogeneous Catalyst for Microwave‐Assisted Suzuki–Miyaura Cross‐Coupling Reaction

“…Iodoanilines 1o and 1p also afforded the expected amino biaryls 2l and 2m in substantial yield. It appeared that there is a report where acetophenone derivatives were not tolerant under Rh‐catalyzed reaction in the presence of nucleophiles 12. Interestingly, in our developed SS‐Rh catalyzed reaction haloacetophenones 1q–s allowed the formation of coupling products 2n–p in good to satisfactory yields.…”

P-Fluorous Phosphines as Electron-Poor/Fluorous Hybrid Functional Ligands for Precious Metal Catalysts: Synthesis of Rh(I), Ir(I), Pt(II), and Au(I) Complexes Bearing P-Fluorous Phosphine Ligands

“…Therefore, we investigated the reaction of a P-perfluoroalkylated phosphine with [RhCl(CO)2]2 for the synthesis of RhCl(CO)(R2PRf)2. When the reaction of 1a or 1b with [RhCl(CO)2]2 was examined according to a reported method [9], RhCl(CO)(Ph2P n C10F21)2 (3a) and RhCl(CO)( n Bu2P n C10F21)2 (3b) were obtained in good yields, respectively (Equation (4)). Coupling in the 31 P NMR spectrum was assigned to the interaction between 31 P and 103 Rh (JP-Rh = 143.8 Hz), confirming complexation between the Pperfluoroalkylated phosphine and rhodium.…”

“…Since strongly electron-withdrawing ligands are known to promote reductive elimination steps in catalytic reactions, the former property may be exploited, not only to optimize known reactions, but also to develop new catalytic reactions [9][10][11][12]. As to the latter property, the use of a fluorous biphasic system (FBS) may make it possible to recover catalysts and ligands easily and to reuse them for catalytic reactions.…”