Xyl-PHANEPHOS

The hydrogenation of a number of aromatic ketones is shown in Figure 37.30. Noyori s very effective Ru-diphosphine-diamine technology was developed by several companies. It is not clear on which scale the processes developed by Takasago (dm-binap = 3,5-xylyl-binap) [16] and Dow/Chirotech [109-111] for the reduction of substituted acetophenones are actually applied commercially. Using the Xyl-PhanePhos-dpen catalyst, a highly efficient bench-scale process was developed for the hydrogenation of p-fluoroacetophenone (ee 98%, TON 100000, TOF 50000 IT1 at r.t., 8 bar) [109]. Ru-P-Phos (licensed to Johnson Matthey [112]) achieved ee-values >99.9% and TON up to 100000 for sev-... 

The ligands tested were tol-binap, dipamp, P-phos, xyl-P-phos, binam, phanephos and xyl-phanephos with the results lised in Table E Table 2 shows the effect which... 

The diamine ligands that have shown the most consistent usage are DPEN (145) and diapen (146). The best bisphosphines ligands used to date have been axial bisphosphines ligands, such as BINAP (3a), tol-BINAP (3b), xyl-BINAP (3c),23 188 xyl-PhanePhos (127b),162 163 and xyl-P-Phos (120c).153... 

A number of bench-scale processes with Ru/P P/N N catalysts are summarized in Fig. 13. Dow/Chirotech [91] used Ru/Xyl-PhanePhos/dpen for the hydrogenation of p-fluoro acetophenone. Kanto Chemicals developed a very effective Ru/bdpp/N N catalyst (the only case where the diphosphine is not a biaryl type) and applied it to the large scale hydrogenation of acetophenone [92] and of a quinuclidine [93] for a muscarinic receptor antagonist. Nycomed/JMC [94] scaled up the hydrogenation of rather complex ketone intermediate for the synthesis of a potassium competitive acid blocker. 

---