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  Approaching sub-ppm-level asymmetric organocatalysis of a highly challenging and scalable carbon–carbon bond forming reaction

Bae, H. Y., Höfler, D., Kaib, P. S. J., Kasaplar, P., De, C. K., Döhring, A., et al. (2018). Approaching sub-ppm-level asymmetric organocatalysis of a highly challenging and scalable carbon–carbon bond forming reaction. Nature Chemistry, 10(8), 888-894. doi:10.1038/s41557-018-0065-0.

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Bae, Hoefler, Kaib, Kasaplar, De, Doehring, Lee, Kaupmees, Leito, List 2018.pdf (Postprint), 2MB
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Bae, Hoefler, Kaib, Kasaplar, De, Doehring, Lee, Kaupmees, Leito, List 2018.pdf
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Bae, Han Yong1, Author           
Höfler, Denis1, Author           
Kaib, Philip S. J.1, Author           
Kasaplar, Pinar1, Author           
De, Chandra Kanta1, Author           
Döhring, Arno1, Author           
Lee, Sunggi1, Author           
Kaupmees, Karl2, Author
Leito, Ivo2, Author
List, Benjamin1, Author           
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1Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445585              
2University of Tartu, Institute of Chemistry, Tartu, Estonia, ou_persistent22              

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 Abstract: The chemical synthesis of organic molecules involves, at its very essence, the creation of carbon–carbon bonds. In this context, the aldol reaction is among the most important synthetic methods, and a wide variety of catalytic and stereoselective versions have been reported. However, aldolizations yielding tertiary aldols, which result from the reaction of an enolate with a ketone, are challenging and only a few catalytic asymmetric Mukaiyama aldol reactions with ketones as electrophiles have been described. These methods typically require relatively high catalyst loadings, deliver substandard enantioselectivity or need special reagents or additives. We now report extremely potent catalysts that readily enable the reaction of silyl ketene acetals with a diverse set of ketones to furnish the corresponding tertiary aldol products in excellent yields and enantioselectivities. Parts per million (ppm) levels of catalyst loadings can be routinely used and provide fast and quantitative product formation in high enantiopurity. In situ spectroscopic studies and acidity measurements suggest a silylium ion based, asymmetric counteranion-directed Lewis acid catalysis mechanism.

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Language(s): eng - English
 Dates: 2017-11-022018-04-112018-07-092018-08-01
 Publication Status: Published in print
 Pages: 7
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1038/s41557-018-0065-0
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Title: Nature Chemistry
  Abbreviation : Nat. Chem.
Source Genre: Journal
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Publ. Info: London, UK : Nature Publishing Group
Pages: - Volume / Issue: 10 (8) Sequence Number: - Start / End Page: 888 - 894 Identifier: ISSN: 1755-4330
CoNE: https://pure.mpg.de/cone/journals/resource/1755-4330