We report a new strategy for the preparation of dirhodium(ii) complexes with the general formula Rh(A) that allows the isolation of a dirhodium tetracarboxylate complex with a free amino group available for postfunctionalization. The postfunctionalization of this complex enables the incorporation of a variety of functional groups, including double and triple bonds as well as nucleophilic moieties, thus paving the way to new classes of polymeric as well as bifunctional catalysts, and polymetallic complexes. Furthermore, we demonstrate that a urea containing dirhodium(ii) complex enables site-selective nitrenoid insertions by remote hydrogen bonding control.
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http://dx.doi.org/10.1039/c8sc05733h | DOI Listing |
J Am Chem Soc
April 2021
Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 34141, South Korea.
Alkanes are an abundant and inexpensive source of hydrocarbons; thus, development of new methods to convert the hydrocarbon feedstocks to value-added chemicals is of high interest. However, it is challenging to achieve such transformation in a direct and selective manner mainly due to the intrinsic inertness of their C-H bonds. We herein report a tailored Cp*Co(III)(LX)-catalyzed efficient and site-selective intermolecular amidation of unactivated hydrocarbons including light alkanes.
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March 2019
Justus Liebig University , Institute of Organic Chemistry, Heinrich-Buff-Ring 17 , 35392 Giessen , Germany . Email: ; Email:
We report a new strategy for the preparation of dirhodium(ii) complexes with the general formula Rh(A) that allows the isolation of a dirhodium tetracarboxylate complex with a free amino group available for postfunctionalization. The postfunctionalization of this complex enables the incorporation of a variety of functional groups, including double and triple bonds as well as nucleophilic moieties, thus paving the way to new classes of polymeric as well as bifunctional catalysts, and polymetallic complexes. Furthermore, we demonstrate that a urea containing dirhodium(ii) complex enables site-selective nitrenoid insertions by remote hydrogen bonding control.
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January 2018
Department of Chemistry , University of Virginia, Charlottesville , Virginia 22904-4319 , USA . Email:
This report details the first organocatalytic method for nitrenoid transfer and its application to intermolecular, site-selective C(sp)-H amination. The method utilizes a trifluoromethyl iminium salt as the catalyst, iminoiodinanes as the nitrogen source, and substrate as the limiting reagent. Activated, benzylic, and aliphatic substrates can all be selectively functionalized in yields up to 87%.
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