Enantioselective C H Amination of Achiral Substrates

The Davies catalyst 14 was also found to be useful for intermolecular cyclizations, 

Of particular note, enantioselective intermolecular allylic amination is also pos sible using this protocol, and no competing aziridination is observed. Cyclic and linear alkenes were selectively aminated with high selectivities (27-31). 

Although the use of chiral aminating reagent in concert with chiral catalysts 

Representative allylic C-H insertions (absolute stereochemistry not reported) 

Remarkable enantiocontrol was obtained using N heterocyclic substrates such as protected indole 34 and pyrazole 38, showing the potential of this method in the synthesis of biologically active chiral amines. Another striking element of this catalyst is its reactivity toward alkene substrates. While rhodium tetracarboxylate catalysts tend to promote both C H insertion and aziridination, the Rh2(S nap)4 (32) is particularly selective for C H insertion, cis Olefins were well tolerated, providing the aminated product in good yield and enantioselectivity (39, 41). However, the use of trans isomers resulted in reduced yield and selectivity (e.g., 40). 

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