Investigation of the Organocatalytic Chlorination of 2-Phenylpropanal.
Autor: | Mohr LM; Department of Chemistry, Aarhus University, 8000, Aarhus, Denmark., McCulley CH; Department of Chemistry, Aarhus University, 8000, Aarhus, Denmark., Blom J; Department of Chemistry, Aarhus University, 8000, Aarhus, Denmark., Lamhauge JN; Department of Chemistry, Aarhus University, 8000, Aarhus, Denmark., Anker Jørgensen K; Department of Chemistry, Aarhus University, 8000, Aarhus, Denmark. |
---|---|
Jazyk: | angličtina |
Zdroj: | Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2021 Dec 09; Vol. 27 (69), pp. 17465-17475. Date of Electronic Publication: 2021 Oct 21. |
DOI: | 10.1002/chem.202103376 |
Abstrakt: | Results of an examination of the organocatalytic enantioselective α-chlorination of 2-phenylpropanal are described. Synthetic investigation including the screening of primary and secondary aminocatalysts, many different reaction conditions, and other α-branched aldehydes show that especially primary aminocatalysts can catalyze the formation of the α-chloro branched aldehydes in good yields, but only with moderate enantioselectivities. In order to try to understand the challenge in obtaining high enantioselectivity for the aminocatalytic α-chlorination of α-branched aldehydes a series of experimental investigations were performed employing 2-phenylpropanal as a model system. These investigations have been coupled with computational investigations, which provided important insight into the moderate enantioselectivity of this chlorination reaction. Analysis of the reaction showed, that the lack of control over the selectivity of formation of the (E)- and (Z)-enamine intermediate, and the clustering of reaction barriers of possible reaction pathways help to rationalize difficulties in producing high enantioselectivity. (© 2021 Wiley-VCH GmbH.) |
Databáze: | MEDLINE |
Externí odkaz: |