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Intramolecular asymmetric reductive amination: synthesis of enantioenriched dibenz[c,e]azepines.

ABSTRACT: An Ir-catalyzed intramolecular asymmetric reductive amination (ARA) of bridged biaryl derivatives has been described. Using this unprecedented approach, synthetically useful dibenz[c,e]azepines containing both central and axial chiralities are obtained with excellent enantiocontrol (up to 97% ee). This methodology represents a rare example of enantioselective chemocatalytic synthesis of chiral dibenz[c,e]azepines featuring a broad substrate scope, and their synthetic utilities are exhibited by derivatizing the products into a chiral amino acid derivative and chiral phosphoramidite ligands, which display excellent enantiocontrol in Rh-catalyzed asymmetric hydrogenation of α-dehydroamino acid derivatives. Remarkably, our method is also applicable to enantioselectively synthesize an allocolchicine analogue.

SUBMITTER: Yang T

PROVIDER: S-EPMC6385856 | biostudies-other | 2019 Feb

REPOSITORIES: biostudies-other

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Intramolecular asymmetric reductive amination: synthesis of enantioenriched dibenz[c,e]azepines.

Yang Tao T Guo Xiaochong X Yin Qin Q Zhang Xumu X

Chemical science 20181227 8

An Ir-catalyzed intramolecular asymmetric reductive amination (ARA) of bridged biaryl derivatives has been described. Using this unprecedented approach, synthetically useful dibenz[c,e]azepines containing both central and axial chiralities are obtained with excellent enantiocontrol (up to 97% ee). This methodology represents a rare example of enantioselective chemocatalytic synthesis of chiral dibenz[c,e]azepines featuring a broad substrate scope, and their synthetic ...[more]

PMID: 30881676

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