期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 134, 期 40, 页码 16869-16876出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja307712y
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资金
- Marie Curie Intra-European Fellowship within the sixth European Community Framework Programme [MEIF-CT2006-040554]
- Marie-Curie Reintegration Grant within the seventh European Community Framework Programme [PERG04-GA-2008-239244]
The mechanism of the reaction between di-tert-butyl azadicarboxylate and 1,3-dicarbonyl compounds catalyzed by an axially chiral guanidine is investigated by density functional theory methods. The results show that the catalyst acts simultaneously as a Bronsted base and an acid catalyst, and the mechanism is similar to that of the related BINOP organocatalysts. Surprisingly, cyclic and acyclic beta-keto esters yield opposite enantiomers; the calculations demonstrate that this is a consequence of the preferred enolate geometry in the transition structures. Literature evidence suggests that other organocatalytic reactions show similar behavior.
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