Racemic potential ligands, resolution

In the early belief that these reactions were completely stereospecific, we felt that the reaction of [Co(1-pn)2CI2]+ with carbonate could not give an optical inversion under any experimental conditions. This is, of course, not true, as was soon shown by the work of McReynolds (28) and Sister Mary Martinette Hagan (29). In a cobalt complex containing asymmetric ligands, one form is preferred, but both forms can and do exist. In the same belief, we hoped that stereospecific effects could be used in the resolution of racemic potential ligands. This does give partial resolution, as shown by the work of Johnson (30),... 

P-chiral phosphines, which are potential ligands for transition metal-catalyzed reactions, were synthesized through hpase-catalyzed optical resolution of the corresponding racemic phosphine oxide compounds (Fig. 10.29). For example, lipase from C. rugosa (CRL) was used for the enantioselective hydrolysis of acetoxynaphthyl phosphine oxide (Fig. 10.29(a)). The P-enantiomer was hydrolyzed selectively, leaving the (S)-acetoxy compound, which was further subjected to chemical hydrolysis. Both enantiomeric phosphine oxides were obtained in >95% after recrystallization. Methylation followed by reduction with triethyl amine/trichlorosilane, with inversion of configuration, yielded the desired chiral phosphine. 

The subject of asymmetric synthesis generally (214, 215) gained new momentum with the potential use of transition metal complexes as catalysts. The use of a complex with chiral ligands to catalyze a synthesis asymmetrically from a prochiral substrate is advantageous in that resolution of a normally obtained racemate product may be avoided, for example,... 

Trefoil knots, and therefore the molecular knots discussed in this section, are chiral (Figure 4-29). The resolution of a dicopper(I) knot prepared from a helical precursor containing the 1,3-phenylene-linked bis-phenanthroline ligand described above (LI 198) has been achieved by crystallisation of the racemic cation with (5)-(+)-l,l -binaphthyl-2,2 -diyl phosphate [343]. As commented by these authors, the preparation of optically pure knot complexes is of great potential interest in relation both to interactions with biological molecules and, where the complexed metal has more than one accessible oxidation state, to enantioselective electron transfer [344]. 

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