Acetic acid aldol reactions in the presence of trimethylsilyl trifluoromethanesulfonate

Journal of Organic Chemistry

Volumn 75, Issue 15, 2010, Pages 5351-5354

  Downey, C Wade ^a   Johnson, Miles W ^a   Lawrence, Daniel H ^a   Fleisher, Alan S ^a   Tracy, Kathryn J ^a  

^a UNIVERSITY OF RICHMOND   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDOL ADDITION; ALDOL REACTIONS; ESTER FORMATION; IN-SITU; MUKAIYAMA ALDOLS; ONE POT PROCESS; SILYL KETENE ACETAL FORMATION; TRIALKYLAMINE; TRIMETHYLSILYL;

ALDEHYDES; CARBOXYLIC ACIDS; ESTERS; ORGANIC ACIDS; PH EFFECTS;

ACETIC ACID;

ACETIC ACID; KETENE DERIVATIVE; TRIFLUOROMETHANESULFONIC ACID; TRIFLUOROMETHANESULFONIC ACID TRIMETHYLSILYL ESTER; TRIMETHYLSILYL DERIVATIVE; UNCLASSIFIED DRUG;

ALDOL REACTION; ARTICLE; CHEMICAL ANALYSIS; CHEMICAL STRUCTURE; MUKAIYAMA REACTION; ONE POT SYNTHESIS;

EID: 77955164505     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo100828c     Document Type: Article

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17. Although methanol was also an effective solvent for the desilylation reaction, competing formation of the methyl ester via Fischer esterification was observed.
18. We speculate that the nitro group may interact unfavorably with the TMSOTf catalyst, although addition of 1.4 equiv of nitrobenzene to the standard reaction with benzaldehyde does not affect conversion for that substrate. Note that the other electron-poor aromatic aldehyde tested, 4-fluorobenzaldehyde, reacts in high yield.
19. Addition of tetrabutylammonium salts as phase transfer catalysts had no effect upon reaction converstion.
20. 1H NMR spectra for the stereoisomers of compound 12.
21. Because of the symmetry of the bis-silyl ketene acetal derived from a carboxylic acid under these conditions, enolization can only produce a compound of Z geometry.