Imino‐ and Oxazolino‐Functionalised Pyrrolylphosphanes and Pyrrolylphosphinites: An Unexploited Class of Chiral P,N‐Bidentate Ligands with Unusual Electronic Properties

Diastereomeric P*-mono- and P*,P*-bidentate diamidophosphite ligands based on 1,4:3,6-dianhydro-d-mannitol in asymmetric metallocomplex catalysis

“…31 In all cases, "natural" diastereomer (S C ,R P ) 4 pro vides much higher ee values of products 14, 16, and 18 (and sometimes the conversion of the starting substrates) than (R C ,S P ) 4. The use of the both isomers of ligand 4 makes it possible to obtain products 14 and 18 with the opposite absolute configurations (see Table 2, entries 1-4 and 9-11).…”

“…In the 31 P NMR spectra, the signals of compounds 10 and 12 are narrow symmetric singlets, indicating either the fast mutual transformation of their exo and endo isomers, or the absence of one of them (see Ref. 31).…”

“…Experimental31 P and 13 C NMR spectra were recorded on a Bruker Avance 400 instrument (161.98 and 100.61 MHz) relative to 85% H 3 PO 4 in D 2 O and CDCl 3 (δ C 76.91), respectively. Signals in the 13 C NMR spectra were assigned using the J modulated echo procedure.…”

Coordination chemistry and applications of metal phenolates containing an oxazoline group

“…A chiral congener of this series, 2-[(4S)-4,5-dihydro-4-benzyl-2-oxazolinyl]phenol, has likewise recently been characterised in a similar way (Luo et al 2010). This compound and its derivatives have found use in the design of larger ligand Brought to you by | University of Michigan Authenticated Download Date | 6/15/15 3:26 PM frameworks, such as oxazolinyl-functionalised pyrrolylphosphines (Gavrilov et al 2004(Gavrilov et al , 2005, and are useful precursors for the formation of functionalised polymers (Wörner et al 1995;Lustoň et al 2006), liquid crystals (Serrano et al 1995), and as molecules for the selective detection of metals such as Zn via formation of metal-phenolate complexes (Zhang et al 2004;Son et al 2008). …”

Synthesis of a rhodium(I) carbonyl complex with a chiral aminodiphosphine ligand and its immobilization onto aminopropyl functionalized silica gel

“…However, compared to simple diphosphine ligands, mixed donor ligands bearing a soft and hard combination of donors in the same ligand framework (e.g., PO, PN, POP, and PNP) have an additional advantage because of their hemilabile behavior [9][10][11]. In fact, chiral P,O and P,N donor hemilabile ligands have been used in asymmetric catalysis [3,[12][13][14][15], e.g., Polo et al [14] reported a Rh(I) complex with enantiomerically pure hydroxylated phosphine, (1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol and its catalytic activity for hydroformylation of olefin and Tsarev et al [15] reported rhodium and palladium complexes with chiral P,N-bidentate ligands with the palladium complexes showing enantioselectivity up to 93% for asymmetric alkylation.…”