Ligands, chiral reaction

Another important reaction associated with the name of Sharpless is the so-called Sharpless dihydroxylation i.e. the asymmetric dihydroxylation of alkenes upon treatment with osmium tetroxide in the presence of a cinchona alkaloid, such as dihydroquinine, dihydroquinidine or derivatives thereof, as the chiral ligand. This reaction is of wide applicability for the enantioselective dihydroxylation of alkenes, since it does not require additional functional groups in the substrate molecule ... 

The first example of asymmetric catalytic ring-opening of epoxides with sp2-hybridized carbon-centered nucleophiles was reported by Oguni, who demonstrated that phenyllithium and a chiral Schiff base ligand undergo reaction to form a stable system that can be used to catalyze the enantioselective addition of phenyllithium to meso-epoxides (Scheme 7.24) [48]. Oguni proposed that phenyllithium... 

When the Pd bears chiral ligands, these reactions can be enantioselective. TT-Allylmolybdenum compounds behave similarly.Because palladium compounds are expensive, a catalytic synthesis, which uses much smaller amounts of the complex, was developed. That is, a substrate such as an allylic acetate, carbo-... 

N-donor ligand. The reaction appears to proceed via an acyclic iminoplatinum(II) intermediate that undergoes a subsequent intramolecular cyclization. Some mechanistic aspects of this versatile reaction have been elucidated.225,226 A4-l,2,4-oxadiazolines have been prepared by the [2+3] cycloaddition of various nitrones to coordinated benzonitrile in m-[PtCl2( D M SO)(PhCN)] precursors.227,228 Racemic and chiral [PtCl2(PhMeSO)(PhCN)] complexes have also been used in order to introduce a degree of stereoselectivity into the reaction, resulting in the first enantioselective synthesis of A4-l,2,4-oxadiazolines, which can be liberated from the complexes by the addition of excess ethane-1,2-diamine. 

The phosphetane ring is a useful synthon in the preparation of optically active ligands. Chiral l,2-bis(phosphetano)benzenes 38 are easily prepared from dilithiophenylphosphine 36 by reaction with a cyclic sulfate 37 <00T95>. 

During the late 1960s, Homer et al. [13] and Knowles and Sabacky [14] independently found that a chiral monodentate tertiary phosphine, in the presence of a rhodium complex, could provide enantioselective induction for a hydrogenation, although the amount of induction was small [15-20]. The chiral phosphine ligand replaced the triphenylphosphine in a Wilkinson-type catalyst [10, 21, 22]. At about this time, it was also found that [Rh(COD)2]+ or [Rh(NBD)2]+ could be used as catalyst precursors, without the need to perform ligand exchange reactions [23]. 

Scheme 6.30. Zr-catalyzed enantioseiective Mannich reactions with chiral VAPOL ligands remarkably, reactions remain as enantioseiective at 100 °C as they are at 25 °C. Deprotection to give the fi-amino ester is carried out in a single step.

Table 19 reports multicollisional dissociation thresholds of the selected complexes. A direct correlation exists between them and the proton affinity (PA) of the guest. However, although chiral specificity has been observed in similar systems using ligand-exchange reactions (see previous sections), the results of Table 19 show no such specificity. The differences in binding of the Ala and Phe enantiomers are evidently too small to be measured with this method. 

Abstract Several bismuth-catalyzed synthetic reactions, which proceed well in aqueous media, are discussed. Due to increasing demand of water as a solvent in organic synthesis, catalysts that can be used in aqueous media are becoming more and more important. Although bismuth Lewis acids are not very stable in water, it has been revealed that they can be stabilized by basic ligands. Chiral amine and related basic ligands combined with bismuth Lewis acids are particularly useful in asymmetric catalysis in aqueous media. On the other hand, bismuth hydroxide is stable and works as an efficient catalyst for carbon-carbon bond-forming reactions in water. 

In summary, the configuration of the desired product is controlled by the planar-chiral imine and ketimine ligand backbone. The selectivity of the reaction depends on both the chiral center and the communication of the side-chain with the ligand backbone. We tuned the side-chain to increase the enantioselectivity up to 90% ee. In the case of the amino alcohol ligands, chiral cooperativity is also observed. However, the influence of the planar chirality is much lower, whereas central chirality is dominant in this instance. In most cases the enantioselectivity is lower than for the ketimines. 

As another approach, Carreira and coworkers reported the alkynylation of a nitrone using a terminal alkyne and catalytic amounts of Zn(OTf)2 and amine135. In the presence of a chiral ligand, the reaction proceeds enantioselectively to give hydroxyamine with . 

When the Pd bears chiral ligands, these reactions can be enantioselective.1448 ir-Allylmo-lybdenum compounds behave similarly.1449 Because palladium compounds are expensive, a catalytic synthesis, which uses much smaller amounts of the complex, was developed. That is, a substrate such as an allylic acetate, alcohol, amine, or nitro compound1450 is treated with the nucleophile, and a catalytic amount of a palladium salt is added. The rr-allylpal-ladium complex is generated in situ. Alkene-palladium complexes (introducing the nucleophile at a vinylic rather than an allylic carbon) can also be used.1451... 

To achieve the desired asymmetric induction, chirality must be introduced. There are essentially three ways to do this. One can employ (i) chirally modified substrates (ii) chirally modified nucleophiles or (iii) a chiral reaction medium (chiral coordinating cosolvents, ligands or catalysts). This chapter is organized according to these three approaches. 

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