P-Phos:  A Family of Versatile and Effective Atropisomeric Dipyridylphosphine Ligands in Asymmetric Catalysis

Abstract

This Account outlines our efforts in the design and synthesis of a family of highly effective atropisomeric dipyridylphosphine ligands (P-Phos and its variants) and in the development of their widespread applications in transition-metal-catalyzed asymmetric reactions including hydrogenation, hydrosilylation, and C-C bond formation. Desirable attributes, such as air stability, broad substrate scope, fast rates of reaction, excellent enantioselectivities, low catalyst loading, and mild conditions, make the catalyst systems highly attractive and thus may provide excellent opportunities for practical applications.

Effective Chiral Ferrocenyl Phosphine‐Thioether Ligands in Enantioselective Palladium‐Catalyzed Allylic Alkylations

“…[9] According to the recent works by Carretero and coworkers, [10] Fesulphos which contained only planar The development of highly efficient and practical chiral ligands for asymmetric C À C bond formation is a long-standing research interest for many scientists. Previously we showed that chiral diphosphine ligands P-Phos [11] with heteroaromatic scaffolds are excellent ligands for asymmetric hydrogenations [12] as well as some C À C bond formation reactions. [13] Notably, these ligands are air-stable compared to the analogous BINAP ligand.…”

3,3′-Bipyridine, 4,4′-bis[bis(3,5-dimethylphenyl)phosphino]-2,2′,6,6′-tetramethoxy-, (3R)-; 3,3′-bipyridine, 4,4′-bis[bis(3,5-dimethylphenyl)phosphino]-2,2′,6,6′-tetramethoxy-, (3S)-

“…The rhodium(I) catalyst formed in situ from [Rh(COD)OH] 2 and Xyl-P-Phos promoted S N 2 allylic substitution with a variety of arylboronic acids with up to 92% ee and >20:1 regioselectivity. 17 2 12 mol % (S)-1 20 mol % AgBF 4 (10)…”

Synthesis of Bis(2-Pyridylphosphino)Alkanes in Superbasic Medium and Their Hydroxymethyl Derivatives

“…Pyridyl diphosphines have been shown to display various coordination modes: they serve as useful building blocks for di-and polynuclear compounds (MOFs) and have catalytic applications. 4,5 It has been shown recently that secondary diphosphines are excellent precursors for 14-, 16-, 18-, and 20-membered macrocycles. [6][7][8] Here, we present the synthesis of novel pyridyl substituted P-H-diphosphines 1-3 by the reaction of primary pyridyl phosphine with 1,3-dichloropropane, 1,4-dichlorobutane, and 1,5-dichloropentane in potassium hydroxide (KOH)/dimethyl sulfoxide (DMSO) medium in moderate (in the case of 2) or good (in the case of 1 and 3) yields (Scheme 1).…”