Oxazoline-based chiral ligands

QM/MM calculations and experimental kinetic study have explored the effects of solvation on the transition states for reaction between nitromethane and formaldehyde and between nitropropane and benzaldehyde. Asymmetric reactions of nitromethane with various aldehydes have been promoted by Cu(II) coordinated with amino alcohols, 0 imidazolium/pyrrolidinium-tagged Indabox, and imidazolium-taggedbis(oxazoline)-based chiral ligands. The Henry reaction has also been promoted by Mn(OAc)2/Schiff bases bearing a triazole structure, with up to 99% yield, and by phosphonium ionic ligands MeP+(octyl)3 R0C02 without solvent. ... 

Fig. 5 Examples of quenching enantioselective sensors involving metal ions (a) JV.W -dioxide of the 1,8-diacridylnaphtalene units which can form a scandium(m) complex (b) high enantioselective quenching obtained by the scandium complex of 11 for 2-aminopropanol (reprinted with permission from [64]. Copyright 2008 American Chemical Society) (c) triamino-diamido copper (II) complex (12) (d) Zn (II) complex with terpyridine based chiral ligand (13) (e) chiral oxazoline containing maleimido polymers (14)...

Asymmetric allylic oxidation and benzylic oxidation (Kharasch-PSosnovsky reaction) are important synthetic strategies for constructing chiral C—O bonds via C—H bond activation.In the mid-1990s, the asymmetric Kharasch-Sosnovsky reaction was first studied by using chiral C2-symmetric bis(oxazoline)s. " Later various chiral ligands, based mainly on oxazoline derivatives and proline derivatives, were used in such asymmetric oxidation. Although many efforts have been made to improve the enantioselective Kharasch-Sosnovsky oxidation reaction, most cases suffered from low to moderate enantioselectivities or low reactivities. 

In this paper we have described a design approach for heterogeneous enantioselective catalysts. The approach is based upon modification of the counter-cation of zeolites or mesoporous alumino-silicates with a suitable chiral ligand.7 We have demonstrated the approach with two examples (a) enantioselective aziridination of alkenes using Cu2+-exchanged zeolite Y modified with chiral oxazolines and (b) the modification of... 

The chiral nitrogen-phosphine ligands represent the most flourishing bitopic auxiliaries. They can be divided into five classes closely related to their skeletons, which are binaphtyl-, pyridine-, metallocene-, amine-, or oxazoline-based. Much attention has been given to the last class, which has led to a spectacular... 

The extraction concept is also applicable to sophisticated syntheses of fine-chemicals as recently shown by Ohe, Uemura and co-workers [35], They prepared a novel amphiphilic phosphinite-oxazoline chiral ligand based on D-glucosamine. The corresponding palladium complex was an efficient catalyst for asymmetric allylic substitution reactions and could be recycled by simple acid/base extraction and reused in the second reaction without loss of enantioselectivity. 

Serrano and co-workers have reported the synthesis of two interesting series of chiral, hexacatenar metal complexes, that is, mono- and dinuclear, derived from chiral oxazoline-based ligands.None of the pure dinuclear compounds (136 X = OAc, Cl) was mesomorphic and most were room-temperature oils or glassy materials. This is likely due to the sterically demanding central chiral unit preventing molecular stacking and, hence, mesophase formation. 

Transition metal-catalysed methods for carbenoid insertion into C-H bonds remain well documented. The asymmetric intramolecular Cu(II)-catalysed C-H insertion reactions of (i) a-diazo-/ -keto esters and phosphonates and (ii) a-diazo sulfones have been described. One can note that the optimal reaction conditions have been found to be quite similar regardless of the nature of the carbenoid precursor the best conditions featured CUCI2 as Cu(II)-source, bis(oxazoline) (68) as chiral ligand and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl] borate (i.e., NaBARF) as additive. Under the so-optimized reaction conditions, each of these carbenoid sources have been eonverted into five-membered cyclopentanone-based derivatives (69), whereas a-sulfonyl diazo esters (70) have led to six-membered cyclic compounds (71), thus featuring a distinct but well-known selectivity. In a related work, the asymmetric C-H insertion cyclization of (70) to (71) has also been achieved under Rh(II)-catalysis, using a combination of Rh2(5-pttl)4 (72) as chiral catalyst and menthyl ester as chiral auxiliary. As already mentioned in the previous section, allene-containing substrates (49) have been shown to undergo an intramolecular C-H insertion process under Rh(II)-catalysis. ... 

The first asymmetric copper-catalyzed cyclopropanation using a homogeneous catalyst was reported by Noyori in 1966 [31], This reaction, which allowed the cycloaddition on styrene, was carried out with a chiral Schiff base copper complex and produced poor enantiomeric excess (Fig. 11). Further refinement of the chiral ligands produced later much better catalysts, such as the bis-oxazoline (Box) derivatives, able to provide enantioselectivities up to 99%. 

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