RESUMO
Computed descriptors for acyclic diaminocarbene ligands are developed in the context of a gold catalyzed enantioselective tandem [3,3]-sigmatropic rearrangement-[2+2]-cyclization. Surrogate structures enable the rapid identification of parameters that reveal mechanistic characteristics. The observed selectivity trends are validated in a robust multivariate analysis facilitating the development of a highly enantioselective process.
Assuntos
Alcinos/síntese química , Ciclização , Dioxolanos/síntese química , Ouro/química , Alcinos/química , Catálise , Cristalografia por Raios X , Dioxolanos/química , Ligantes , Modelos Moleculares , Estrutura Molecular , EstereoisomerismoRESUMO
The gold-catalyzed enantioselective hydroazidation and hydroamination reactions of allenes are presented herein. ADC gold(I) catalysts derived from BINAM were critical for achieving high levels of enantioselectivity in both transformations. The sense of enantioinduction is reversed for the two different nucleophiles, allowing access to both enantiomers of the corresponding allylic amines using the same catalyst enantiomer.