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Catalytic diastereo- and enantioselective additions of versatile allyl groups to N-H ketimines.
Catalytic diastereo- and enantioselective additions of versatile allyl groups to N-H ketimines.
- Source :
-
Nature chemistry [Nat Chem] 2017 Dec; Vol. 9 (12), pp. 1269-1275. Date of Electronic Publication: 2017 Jul 17. - Publication Year :
- 2017
-
Abstract
- There are many biologically active organic molecules that contain one or more nitrogen-containing moieties, and broadly applicable and efficient catalytic transformations that deliver them diastereoselectively and/or enantioselectively are much sought after. Various methods for enantioselective synthesis of α-secondary amines are available (for example, from additions to protected/activated aldimines), but those involving ketimines are much less common. There are no reported additions of carbon-based nucleophiles to unprotected/unactivated (or N-H) ketimines. Here, we report a catalytic, diastereo- and enantioselective three-component strategy for merging an N-H ketimine, a monosubstituted allene and B <subscript>2</subscript> (pin) <subscript>2</subscript> , affording products in up to 95% yield, >98% diastereoselectivity and >99:1 enantiomeric ratio. The utility of the approach is highlighted by synthesis of the tricyclic core of a class of compounds that have been shown to possess anti-Alzheimer activity. Stereochemical models developed with the aid of density functional theory calculations, which account for the observed trends and levels of enantioselectivity, are presented.
Details
- Language :
- English
- ISSN :
- 1755-4349
- Volume :
- 9
- Issue :
- 12
- Database :
- MEDLINE
- Journal :
- Nature chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 29168479
- Full Text :
- https://doi.org/10.1038/nchem.2816