| Autor: |
Rezayee NM; Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark., Rusbjerg M; Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark., Marx M; Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark., Linde ST; Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark., Jørgensen KA; Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark. |
| Jazyk: |
angličtina |
| Zdroj: |
The Journal of organic chemistry [J Org Chem] 2022 Feb 04; Vol. 87 (3), pp. 1756-1766. Date of Electronic Publication: 2021 Oct 05. |
| DOI: |
10.1021/acs.joc.1c01937 |
| Abstrakt: |
This article discloses the direct α-amination of α-branched aldehydes applying nitrogen-based nucleophiles. Under organocatalyzed, oxidative conditions α-branched aldehydes are umpoled to their electrophilic synthons and, subsequently, displaced by a variety of nucleophilic amines to form tetrasubstituted tertiary centers. A similar strategy has been previously employed to form congested C-C, C-O, and C-S bonds; however, unsatisfactory results were received when extending the methodology to include C-N bonds. Initially, intramolecular α-amination reactions were undertaken to foster dihydroquinoxaline-type products. A solvent exchange to the polar, aprotic solvent, MeNO 2 , proved critical to facilitate intermolecular α-C-N bond formation with a wide range of amine coupling partners ( N -heterocycles, N,N -diaryl amines, and anilines). Application of the solvent exchange to the enantioselective S N 2-DKR manifold provided distinct regimes leading to refinement in yield and enantioselectivity. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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