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Zusammenfassung:
Titanation of alkyllithium or -magnesium compounds using ClTi(OR)3 results in reagents which show markedly increased diastereofacial selectivity (80–90%) in reactions with α-chiral aldehydes or ketones. Titanation is also the method of choice in Grignard-type additions to substituted cyclohexanones; CH3Ti(OCHMe2)3 (6a) adds predominantly from the equatorial direction, while allyltitanium reagents 11b and 12 show axial preference. Crotyltitanium compounds react with carbonyl compounds to afford primarily adducts having anti-configuration, a process which is of particular value in case of ketones (anti/syn ratios up to 99:1). Titanation of (trimethylsilyl)allyllithium (48) with Ti(OCHMe2)4 reverses regioselectivity in reactions with aldehydes and ketones, β-hydroxy silanes 50 being the only observed products. These have anti-configuration and can be converted either into Z- or E-dienes using the Peterson elimination under basic or acidic conditions, respectively.
