A ruthenium-catalyzed reductive amination without an external hydrogen source has been developed using carbon monoxide as the reductant and ruthenium(III) chloride (0.008-2 mol %) as the catalyst. The method was applied to the synthesis of antianxiety agent ladasten.
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http://dx.doi.org/10.1021/ol503595m | DOI Listing |
J Am Chem Soc
December 2024
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
The homogeneous catalytic hydrogenation of benzo-fused heteroarenes generally provides partially hydrogenated products wherein the heteroaryl ring is preferentially reduced, such as quinoline hydrogenation, leading to 1,2,3,4-tetrahydroquinoline. Herein, we report a carbocycle-selective hydrogenation of fused -heteroarenes (quinoline, isoquinoline, quinoxaline, etc.) using the Ru complex of a chiral spiroketal-based diphosphine (SKP) as the catalyst, affording the corresponding 5,6,7,8-tetrahydro products in high chemoselectivities.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR, China.
Hydroboration of allenes is powerful and atom-economic approach to the synthesis of organoboranes, such as the highly versatile allylboranes. However, regarding regiocontrol, existing methods uniformly deliver the boron functionality to the less hindered β- or γ-position, but not the α-position. The latter is particularly challenging for allenes with substantial steric difference between the two terminals and lacking electronic bias (e.
View Article and Find Full Text PDFJ Org Chem
September 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India.
Until now, a myriad of effective approaches have emerged for the functionalization of -heteroaryl C-H bonds. In contrast, dearomatization and construction of fused heterocycles from activated heteroarenes is still a subject to explore. In this work, we present a refined approach for both dearomatization of -heteroarenes and the synthesis of fused heterocycles from activated heteroarenes ruthenium catalysis using paraformaldehyde along with additive and base.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
Instituto Investigaciones Químicas (CSIC-US), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Américo Vespucio 49, 41092, Sevilla, Spain.
A ruthenium-catalyzed reductive amination via asymmetric transfer hydrogenation (ATH) has been used to perform an efficient dynamic kinetic resolution (DKR) of N-aryl 2-formyl pyrroles decorated with a phosphine moiety positioned at the ortho' position. The strategy relies on the labilization of the stereogenic axis in the substrate facilitated by a transient Lewis acid-base interaction (LABI) between the carbonyl carbon and the phosphorus center. The reaction features broad substrate scope of aliphatic amines and N-aryl pyrrole scaffolds, and proceeds under very mild conditions to afford P,N atropisomers in good to high yields and excellent enantioselectivities (up to 99 % ee) for both diphenyl and dicyclohexylphosphino derivatives.
View Article and Find Full Text PDFJ Org Chem
June 2024
Faculty of Sciences, Department of Chemistry, University of Chile, Las Palmeras 3425, Ñuñoa, Santiago 775000, Chile.
The mono -alkylation of arylamines using alkylamines as alkyl group donors has been scarcely investigated. In this work, we report the mono -alkylation of several arylamines (52-95%) catalyzed by the complex ruthenium-triphos in the presence of Al(OTf). Moreover, the highly reductant ability of the catalyst system allows the tandem reduction/-alkylation of nitrobenzenes in good yields (up to 80%).
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