Organometals chiral

Chodkiewicz, W., One-pot synthesis of chiral phosphonous esters, conversion into asymmetric phosphines, ]. Organomet. Chem., 273, C55, 1984. 

O. Loiseleur, M. Hayashi, M. Keenan, N. Schmees, A. Pfaltz, Enantioselective Heck Reactions using Chiral PN-Ligands, J. Organomet. Chem. 1999, 576,16-22. 

Ursini, C.V., Dias, G.H.M. and Rodrigues, J.A.R., Ruthenium-catalyzed reduction of racemic tricarbonyl( 7 -aryl ketonejchromium complexes using transfer hydrogenation a simple alternative to the resolution of planar chiral organometallics. J. Organomet. Chem., 2005,690, 3176. 

D. Enders and H. Gielen, Synthesis of Chiral Triazolinylidene and Imidazolinylidene Transition Metal Complexes and First Application in Asymmetric Catalysis, J. Organomet. Chem. 2001, 617, 70. 

Corriu, R. J., Larcher, F., and Royo, G., J. Organomet. Chem. 104, 161 (1976) (Synthesis of chiral ferrocenylsilanes stereochemistry of their reactions). 

Gade, L.H. and Bellemin-Laponnaz, S. (2007) Chiral N-heterocyclic carbenes as stereodirecting ligands in asymmetric catalysis. Top. Organomet. Chem., 21, 117-157. 

Walborsky, H. M. Banks, R. B. Banks, M. L. A. Duralsamy, M. Stability and oxidative coupling of chiral vinyl- and cydopropylcopper reagents. Formation of a novel dissymmetric diene. Organometallies 1982, 1, 667-674. 

F. R. W. P. Wild, L. Zsolnai, G. Huttner, and H. H. Brintzinger, Synthesis and Molecular Structures of Chiral ausa-Titanocene Derivatives with Bridged Tetrahydroin-denyl Ligands, J. Organomet. Chem. 232, 233-247 (1982). 

For an excellent review concerning chiral tetrahedral organotransition metal compounds, see Brunner, H. Adv. Organomet. Chem. 18, 151 (1980)... 

Asymmetric synthesis I. Ojima, Catalytic asymmetric synthesis, Wiley, New York, 2000. Chirality in organometallic chemistry R. D. Adams, ed., J. Organomet. Chem., 2006, 691, 10. 

Ketobases possessing a chiral center give rise to diastcreomeric mixtures of aminoalcohols upon organometal addition (Fig. 115). The same occurs when the asymmetric induction center is located on the reagent (see below). 

The most frequently performed reaction with organometals concerns the well-known addition to the carbonyl group of ketobases. This reaction (Fig. 114) exhibits many affinities with reduction, as it affords an aminoalcohol (296), in this case tertiary, and involves analogous stereochemical features when chiral ketobases are employed. Again, the aminoalcohols produced can be further converted, by dehydration, into allylamines (R R C=CH—CHi—N<), which are useful in pharmaceutical chemistry. - ... 

Interesting results are provided by reactions performed with the chiral organometal reagent deriving from the a-bromo ester 301 and zinc (Reformatsky reaction) (Fig. 116), which produces the diastereomeric hydroxy-aminocsters 303 from the achiral (3-ami-nopropiophenones 302. 

In the alkylation of a-chiral aldehydes with no ability to chelate with organometal-lic compounds such as Grignard reagents, erythro alcohols are usually obtained preferentially according to the Cram s rule [127], and high Cram selectivity can be achieved with alkyltitanium reagents developed by Reetz [128]. In contrast, application of amphiphilic alkylation to a-chiral aldehydes enables one to achieve the hitherto difficult anti-Cram selectivity, affording threo alcohols selectively as shown in Sch. 91 [125]. 

In relation to the synthesis of chain molecules with a series of asymmetric centers, macrolides or polyether antibiotics, asymmetric induction in the addition reactions of organometals to chiral aldehydes... 

Hannig F, Kehr G, Frohhch R, et al. Formation of chiral ionic liquids and imidazol-2-yhdene metal complexes from the proteinogenic ami-noacid 1-histidine. J. Organomet. Chem. 2005. 690, 5959-5972. 

Bianchi, M., Matteoli, U., Menchi, G., Frediani, P., Piacenti, F. Asymmetric synthesis by chiral ruthenium complexes. VIII. The asymmetric Cannizzaro reaction. J. Organomet. Chem. 1982, 240, 65-70. 

Emziane, M., Sutowardoyo, K. I., Sinou, D. Asymmetric ring-opening of cyclohexene oxide with trimethylsilyl azide in the presence of titanium isopropoxide/chiral ligand. J. Organomet. Chem. 1988, 346, C7-C10. 

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