Catalytic Asymmetric Intermolecular Stetter Reactions of Enolizable Aldehydes with Nitrostyrenes: Computational Study Provides Insight into the Success of the Catalyst

Fluorine helps: A fluorinated triazolium salt precatalyst has been developed that efficiently promotes the asymmetric intermolecular Stetter reaction of enolizable aldehydes and nitrostyrenes (see scheme). Trans fluorination of the catalyst architecture results in unparalleled reactivity and enantio...

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Published inAngewandte Chemie International Edition Vol. 51; no. 10; pp. 2391 - 2394
Main Authors DiRocco, Daniel A., Noey, Elizabeth L., Houk, K. N., Rovis, Tomislav
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 05.03.2012
WILEY‐VCH Verlag
Wiley
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
Alcohols - chemistry
Aldehydes
Aldehydes - chemistry
Alkenes - chemistry
Asymmetry
Catalysis
Catalysts
Chemistry
Chemistry, Multidisciplinary
Computation
Computer Simulation
density functional calculations
Electrostatics
Fluorination
Fluorine
Molecular Structure
N-heterocyclic carbenes
organocatalysis
Physical Sciences
Science & Technology
Stereoisomerism
Stetter reaction
Styrenes - chemistry
Transformations
organocatalysis
DENSITY FUNCTIONALS
density functional calculations
HETEROCYCLIC ALDEHYDES
Stetter reaction
CARBENES
fluorination
ENERGIES
N-heterocyclic carbenes
ENALS
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Summary:Fluorine helps: A fluorinated triazolium salt precatalyst has been developed that efficiently promotes the asymmetric intermolecular Stetter reaction of enolizable aldehydes and nitrostyrenes (see scheme). Trans fluorination of the catalyst architecture results in unparalleled reactivity and enantioselectivity in the desired transformation. A DFT study provides evidence of an electrostatic interaction as the source of the increased enantio‐induction.
Bibliography:NIGMS - No. GM 36700; No. GM 72586
Amgen
Roche
National Institutes of Health Chemistry-Biology Interface Training Program Grant - No. T32M008496
National Science Foundation - No. CHE-0548209; No. CHE-0400414
ark:/67375/WNG-25RRFRTL-W
istex:3AB7C9374639980D9BCE0D61D2E753C3A6AF999D
We thank NIGMS for generous support of this research (GM 36700 to K.N.H. and GM 72586 to T.R.). T.R. thanks Amgen and Roche for unrestricted support. E.L.N. is grateful to the National Institutes of Health Chemistry-Biology Interface Training Program Grant (T32M008496). K.N.H. is grateful to the National Science Foundation (CHE-0548209) for financial support, to the UCLA Academic Technology Services (ATS) Hoffman2 and IDRE clusters for computational resources, and for the TeraGrid resources provided by NCSA (CHE-0400414).
ArticleID:ANIE201107597
We thank NIGMS for generous support of this research (GM 36700 to K.N.H. and GM 72586 to T.R.). T.R. thanks Amgen and Roche for unrestricted support. E.L.N. is grateful to the National Institutes of Health Chemistry‐Biology Interface Training Program Grant (T32M008496). K.N.H. is grateful to the National Science Foundation (CHE‐0548209) for financial support, to the UCLA Academic Technology Services (ATS) Hoffman2 and IDRE clusters for computational resources, and for the TeraGrid resources provided by NCSA (CHE‐0400414).
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.201107597