Asymmetric epoxidation chiral metal complex catalysis

Taken together, these results for epoxide opening promoted by chiral metal complexes [21] illustrate how much there is find out about asymmetric catalysis by transition metals. These valuable new processes are further proof, if any is required, of the rewards of searching for new reactivity amongst the transition metals. 

This chapter focuses on several recent topics of novel catalyst design with metal complexes on oxide surfaces for selective catalysis, such as stQbene epoxidation, asymmetric BINOL synthesis, shape-selective aUcene hydrogenation and selective benzene-to-phenol synthesis, which have been achieved by novel strategies for the creation of active structures at oxide surfaces such as surface isolation and creation of unsaturated Ru complexes, chiral self-dimerization of supported V complexes, molecular imprinting of supported Rh complexes, and in situ synthesis of Re clusters in zeolite pores (Figure 10.1). 

One of the most exciting developments in asymmetric catalysis over the past 25 years has been the discovery of transition metal complexes that catalyze the oxidation of alkenes to chiral epoxides and 1,2-diols. Equations 12.16, 12.17, and 12.18 show examples of epoxidation and 1,2-dihydroxylation. 

Reaction with alkaline peroxide (or hypochlorite) and a chiral catalyst allows the asymmetric epoxidation of enones. Excellent asymmetric induction has been achieved using metal-chiral ligand complexes, such as those derived from lanthanides and (/ )- or (5)-BlNOL. Alternatively, phase-transfer catalysis using ammonium salt derivatives of Cinchona alkaloids, or the use of polyanuno acid... 

Especially noteworthy is the field of asymmetric catalysis. Asymmetric catalytic reactions with transition metal complexes are used advantageously for hydrogenation, cyclization, codimerization, alkylation, epoxidation, hydroformylation, hydroesterification, hydrosilylation, hydrocyanation, and isomerization. In many cases, even higher regio- and stereoselectivities are required. Fundamental investigations of the mechanism of chirality transfer are also of interest. New chiral ligands that are suitable for catalytic processes are needed. 

This year has again emphasized the growing importance of organo-transition metal complexes in organic synthesis. In catalysed reactions the major advances have been in asymmetric catalysis with the first reports of chiral induction in catalytic epoxidation and further reports on improved catalysts for asymmetric hydrogenation and allylic alkylation. The formation of carbon-carbon bonds continues to attract attention, and several novel and potentially useful synthetic applications of organometallic complexes have been reported. 

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