Enantioselective Ruthenium-Catalyzed C–H Alkylations by a Chiral Carboxylic Acid with Attractive Dispersive Interactions

Asymmetric ruthenium-catalyzed C–H alkylations were enabled by a chiral C2-symmetric carboxylic acid. The mild cooperative ruthenium­(II) catalysis set the stage for the assembly of chiral tetrahydrocarbazoles and cyclohepta­[b]­indoles with high levels of enantioselectivity at room temperature. Mec...

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Bibliographic Details
Published inOrganic letters Vol. 23; no. 7; pp. 2760 - 2765
Main Authors Dhawa, Uttam, Connon, Robert, Oliveira, João C. A, Steinbock, Ralf, Ackermann, Lutz
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 02.04.2021
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
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Summary:Asymmetric ruthenium-catalyzed C–H alkylations were enabled by a chiral C2-symmetric carboxylic acid. The mild cooperative ruthenium­(II) catalysis set the stage for the assembly of chiral tetrahydrocarbazoles and cyclohepta­[b]­indoles with high levels of enantioselectivity at room temperature. Mechanistic studies by experiment and computation identified a fast C–H ruthenation, along with a rate- and enantio-determining proto-demetalation. The asymmetric induction was governed by weak attractive secondary dispersion interactions as found in NCI analysis of the key transition states.
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content type line 23
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.1c00615