The Synthesis of Chiral Phosphorus Ligands for use in Homogeneous Metal Catalysis

Abstract

Recent developments in the synthesis of chiral phosphorus ligands are summarized. Main emphasis is given to the multitude of protocols for their synthesis starting from compounds of the chiral pool or by using other easily available chiral starting materials. Besides mono-and bidentate P-ligands hybrid ligands bearing N, O, or olefinic groups as second ligating units are addressed. The syntheses of new P-chirogenic ligands, as well as ligands with supramolecular structures are likewise reviewed. In appropriate cases structures of related privileged ligands are given for comparison. When available, the efficiency of the new ligands for metal catalyzed reactions are briefly assessed.[a] Dr.

Rhodium(III)‐Catalyzed Enantiotopic C−H Activation Enables Access to P‐Chiral Cyclic Phosphinamides

“…One might expect ab etter transfer of chirality during the transformation by as tereogenic phosphorus atom because of its closer proximity to the catalytic center. [6] Methods for their preparation comprise the formation and separation of diastereomeric mixtures,a sw ell as other resolution techniques. [6] Methods for their preparation comprise the formation and separation of diastereomeric mixtures,a sw ell as other resolution techniques.…”

“…Although P-stereogenic ligands were proven very efficient [4] and stereochemically stable, [5] their relatively low number reflects difficulties in their synthesis. [6] Methods for their preparation comprise the formation and separation of diastereomeric mixtures,a sw ell as other resolution techniques. [7] More-recent approaches involve desymmetrization reactions and catalytic asymmetric methods.…”

Synthesis of C2‐Symmetric Diphosphormonoamidites and Their Use as Ligands in Rh‐Catalyzed Hydroformylation: Relationships between Activity and Hydrolysis Stability

“…Therefore, we used an alternative route starting from the relevantd ichloroaminophosphine. [14] Remarkably,p hosphoramidites based on ap iperazine or homopiperazine ring were quite stable during our purification procedure and could be isolated in good yields as white solids. Due to the simplea nd convenient synthesis, we were able to preparet hem on ag ram scale.…”

“…[4] We were pleasedt os ee that some of our best phosphoramidites could rival the catalytic performanceoft his ligand. (17), N2ÀP2 1.6499 (17), O1ÀP1 1.6502 (14), O2ÀP1 1.6484 (14), O3ÀP2 1.6661 (14),O 4 ÀP2 1.6445 (14);C1-N1-P1 124.48 (13), C2-N2-P2 126.22 (14). (5), C37ÀRh11.815(2), N1ÀP1 1.6571 (15), O1ÀP1 1.6223 (13), O2ÀP1 1.6358 (12); C37-Rh1-O4 89.61 (7), O3-Rh1-O48 8.65 (5), C37-Rh1-P1 87.78 (6), O3-Rh1-P1 94.00(4).…”

Synthesis of New BINAP-Based Aminophosphines and Their 31P-NMR Spectroscopy

“…Bidentate N,P-ligands are particularly effective and have been investigated extensively [5][6][7][8]. Among the variety of chiral backbones,…”