Catalytic Asymmetric Intermolecular Stetter Reaction of Heterocyclic Aldehydes with Nitroalkenes: Backbone Fluorination Improves Selectivity

The catalytic asymmetric intermolecular Stetter reaction of heterocyclic aldehydes and nitroalkenes has been developed. We have identified a strong stereoelectronic effect on catalyst structure when a fluorine substituent is placed in the backbone. X-ray structure analysis provides evidence that hyp...

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Published inJournal of the American Chemical Society Vol. 131; no. 31; pp. 10872 - 10874
Main Authors DiRocco, Daniel A, Oberg, Kevin M, Dalton, Derek M, Rovis, Tomislav
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 12.08.2009
Amer Chemical Soc
Subjects
Aldehydes - chemistry
Alkenes - chemistry
Catalysis
Chemistry
Chemistry, Multidisciplinary
Halogenation
Molecular Structure
Nitro Compounds - chemistry
Organic Chemistry Phenomena
Physical Sciences
Science & Technology
Stereoisomerism
SALTS
FLUORIDE
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Summary:The catalytic asymmetric intermolecular Stetter reaction of heterocyclic aldehydes and nitroalkenes has been developed. We have identified a strong stereoelectronic effect on catalyst structure when a fluorine substituent is placed in the backbone. X-ray structure analysis provides evidence that hyperconjugative effects are responsible for a change in conformation in the azolium precatalyst. This new N-heterocyclic carbene precursor bearing fluorine substitution in the backbone results in significantly improved enantioselectivities across a range of substrates.
Bibliography:NIH RePORTER
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ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/ja904375q