Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 24, Pages 8295-8301Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b03291
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Funding
- ACT-C from JST [JPMJCR12YO]
- KAKENHI (Precisely Designed Catalysts with Customized Scaffolding) from JSPS [25713002, JP16H01043]
- Naito Foundation
- Grants-in-Aid for Scientific Research [16H01043, 25713002, 17H03025] Funding Source: KAKEN
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alpha-Halogenated carbonyl compounds are susceptible to dehalogenation and thus largely neglected as enolate precursors in catalytic enantioselective C-C bond-forming reactions. By merging the increased stability of the alpha-C halogen bond of amides and the direct enolization methodology of the designed amide, we explored a direct catalytic asymmetric Mannich-type reaction of alpha-halo 7-azaindoline amides with N-carbamoyl imines. All alpha-halo substituents, alpha-F, -Cl, -Br, -I amides, were tolerated to provide the Mannich-adducts in a highly stereoselective manner without undesirable dehalogenation. The diastereoselectivity switched intriguingly depending on the substitution pattern of the aromatic imines, which is ascribed to stereochemical differentiation based on the open transition-state model. Functional group interconversion of the 7-azaindoline amide moiety of the Mannich-adducts and further elaboration into a diamide without dehalogenation highlight the synthetic utility of the present protocol for accessing enantioenriched halogenated chemical entities.
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