MOP-Type Binaphthyl Phosphite and Diamidophosphite Ligands and Their Application in Catalytic Asymmetric Transformations

✍ Scribed by Konstantin N. Gavrilov; Sergey E. Lyubimov; Sergey V. Zheglov; Eduard B. Benetsky; Pavel V. Petrovskii; Eugenie A. Rastorguev; Tatiana B. Grishina; Vadim A. Davankov

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 151 KB
• Volume: 349
• Category: Article
• ISSN: 1615-4150
• DOI: 10.1002/adsc.200600340

✦ Synopsis

Abstract

Monodentate phosphite and diamidophosphite ligands have been developed based on O‐methyl‐BINOL. These chiral ligands are easy to prepare from readily accessible phosphorylating reagents – (S~a~ or R~a~)‐2‐chlorodinaphtho[2,1‐d:1′,2′‐f][1,3,2]dioxaphosphepine and (2R,5S)‐2‐chloro‐3‐phenyl‐1,3‐diaza‐2‐phosphabicyclo[3.3.0]octane. The new ligands have demonstrated excellent enantioselectivity in the palladium‐catalysed allylic substitution reactions of (E)‐1,3‐diphenylallyl acetate with sodium p‐toluenesulfinate (up to 99 % ee), pyrrolidine (up to 97 % ee), dipropylamine (up to 95 % ee) and dimethyl malonate (up to 99 % ee). In the palladium‐catalysed deracemization of ethyl (E)‐1,3‐diphenylallyl carbonate, up to 96 % enantioselectivity has been achieved. The diamidophosphite ligands have exhibited very good enantioselectivity in the Rh‐catalysed asymmetric hydrogenation of dimethyl itaconate (up to 90 % ee).