Asymmetric additions to dienes catalysed by a dithiophosphoric acid
| Autor: | Gregory Hamilton, Nathan D. Shapiro, Vivek Rauniyar, F. Dean Toste, Jeffrey Wu |
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| Rok vydání: | 2011 |
| Předmět: |
Indoles
Diene General Science & Technology Markovnikov's rule Chemical Alkenes 010402 general chemistry 01 natural sciences Article Catalysis Mass Spectrometry Phosphates Acid catalysis chemistry.chemical_compound Nucleophile Models Organic chemistry Enantiomeric excess Amination chemistry.chemical_classification Multidisciplinary 010405 organic chemistry Chemistry Alkene Enantioselective synthesis Deuterium 0104 chemical sciences Models Chemical Hydroamination Acids |
| Zdroj: | Nature, vol 470, iss 7333 Nature |
| ISSN: | 1476-4687 0028-0836 |
| DOI: | 10.1038/nature09723 |
| Popis: | Chiral Brønsted acids have become an invaluable tool for achieving a variety of asymmetric chemical transformations under catalytic conditions while avoiding the use of toxic and expensive metals1–8. While the catalysts developed so far are remarkably effective at activating polarized functional groups, chemists have not yet been able to use organic Brønsted acids to catalyze highly enantioselective transformations of unactivated carbon-carbon multiple bonds. This deficiency persists despite the fact that racemic acid-catalyzed “Markovnikov” additions to olefins are a well-established part of the chemist’s toolbox. Here we show that chiral dithiophosphoric acids catalyze the intramolecular hydroamination and hydroarylation of dienes and allenes to generate heterocyclic products in exceptional yield and enantiomeric excess. To help rationalize the unique success of this catalytic system, we present a mechanistic hypothesis that involves the addition of the acid catalyst to the diene followed by SN2′ displacement of the resulting dithiophosphate intermediate. Mass spectrometry and deuterium labelling studies are presented in support of the proposed mechanism. The catalysts and concepts revealed in this study should prove applicable to other asymmetric functionalizations of unsaturated systems. |
| Databáze: | OpenAIRE |
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