Asymmetric Autocatalysis with Organozinc Complexes; Elucidation of the Reaction Pathway

摘要: This review describes the development of mechanistic understanding amplifying asymmetricautocatalysis. After a brief description kinetics, main body work discusses theapplication variety NMR techniques to structure resting state in solution.The results are consistent with dominant square Zn–O bonded dimer at ambient temperature.Furthermore, energies homo- and heterochiral dimers is comparable; they exchange slowly onthe timescale but fast enough for lifetime an individual molecule be established. Theassociation alkylzinc this can quantified located, dynamic alkyl exchangesdefined. DFT calculations have been carried out, which underpin provide furtherinsight into steric control autocatalysis by bulk diisopropylzinc. NMR, kinetics andcomputation converge supporting role indicated structure, pointingto mechanism whereby unique reactivity homochiral driving force, atleast temperature.