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Pd-catalyzed asymmetric allylic alkylations via C-H activation of N-allyl imines with glycinates.

ABSTRACT: Herein is reported the first example of palladium-catalyzed asymmetric allylic alkylation (AAA) reactions involving 2-aza-π-allyl palladium intermediates. The 2-aza-π-allyl complex was generated via a novel mode of activation of N-allyl imines. Pd-catalyzed C(sp³)-H activation of N-allyl imines and subsequent nucleophilic attack by glycinates delivered vicinal diamino derivatives as the sole regioisomers with high levels of diastereo- and enantio-control in the presence of the chiral, bidentate (S,S)-Cy-DIOP ligand. This procedure is highly atom economical and could also be performed by a simple one-pot operation starting from aldehydes, allyl amines and glycinates under mild conditions. The products of this transformation could be converted into various useful derivatives, where the allyl substitution serves as a unique tool for differentiating the two amino moieties in the products.

SUBMITTER: Trost BM

PROVIDER: S-EPMC5643980 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature

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Pd-catalyzed asymmetric allylic alkylations via C-H activation of N-allyl imines with glycinates.

Trost Barry M BM Li Xiaoxun X

Chemical science 20170815 10

Herein is reported the first example of palladium-catalyzed asymmetric allylic alkylation (AAA) reactions involving 2-aza-π-allyl palladium intermediates. The 2-aza-π-allyl complex was generated via a novel mode of activation of N-allyl imines. Pd-catalyzed C(sp3)-H activation of N-allyl imines and subsequent nucleophilic attack by glycinates delivered vicinal diamino derivatives as the sole regioisomers with high levels of diastereo- and enantio-control in the pr ...[more]

PMID: 29147506

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