Fenchyl phosphinites

Enantioselective, palladiumallylic alkylations were studied by experimental and quantum-mechanical methods [316-318]. A number of asymmetric catalysts with varying steric and electronic properties, were synthesized from (—) fenchone, leading to fenchyl phosphinites (FENOPs). These were used for enantioselective allyic alkylations]317]. 

Figure 8.3 Synthesis of modular fenchyl phosphinites (FENOPs) and directed attack of nucleophiles trans to phosphorus In palladium phosphinooxazolines allyl complexes (electronic differentiation) with exo or endo configuration (steric differentiation) [317, 318]. (Reproduced with permission from Ref [317].)...

Figure 8.4 Optimized transition state structure of Pd fenchyl phosphinite, with diphenylallyacetate, leading to enantioselective allylic alkylation (83% ee, Senantiomer). The endo-trans structure shows better Pd-d-7l interaction and less steric repulsion. (Reproduced with permission from Ref [317].)...

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See also in sourсe #XX -- [ ]

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