The palladium-catalyzed hydroarylation of arenediazonium tetrafluoroborates with alkynes in the presence of triphenylsilane affords stereoselectively hydroarylation products in moderate to high yields. The reaction tolerates a variety of substituents including keto, ester, cyano, and nitro groups and can be performed as a one-pot procedure generating the arenediazonium salt in situ. With ethyl phenylpropynoate as the starting alkyne, the hydroarylation affords ethyl (Z)-2-arylcinnamates stereo- and regioselectively.
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http://dx.doi.org/10.1021/ol800266e | DOI Listing |
Chem Pharm Bull (Tokyo)
October 2024
Graduate School of Biomedical and Health Sciences, Hiroshima University.
We studied the reaction pathway of our reductive Heck hydroarylation using a palladium catalyst and a hydrosilane. A key question to verify the reaction mechanism was which active species, Ar-Pd-I or Si-Pd-H, first performs migratory insertion into the alkenes. Identifying this step is crucial to elucidate the reaction mechanism.
View Article and Find Full Text PDFOrg Biomol Chem
October 2024
College of Tobacco Science, Henan Agricultural University, Zhengzhou, 450046, China.
Transition-metal-catalyzed selective hydroarylation of alkynes represents a state-of-the-art approach in organic chemistry. Herein, we report the reaction of symmetrical 1,3-diynes and arylboronic acids, with Pd(OAc) as the catalyst and PCy as the ligand, affording functionalized enynes in good to excellent yields. Its efficiency is demonstrated by its good functional group tolerance and broad substrate scope.
View Article and Find Full Text PDFJ Am Chem Soc
May 2024
Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Lu, Shanghai 200433, China.
Aliphatic strained rings have been increasingly applied in medicinal chemistry due to their beneficial physicochemical and pharmacokinetic properties. However, the divergent synthesis of enantioenriched cyclobutane derivatives with various structural patterns continues to be a significant challenge. Here, we disclose a palladium-catalyzed enantioselective desymmetrization of cyclobutenes, resulting in a series of hydroarylation and 1,2- and 1,3-diarylation products via the interceptions of a common Heck intermediate.
View Article and Find Full Text PDFJ Org Chem
February 2024
Graduate School of Biomedical and Health Sciences, Hiroshima University, 1-2-3 Kasumi, Minami-ku, Hiroshima 734-8553, Japan.
The reductive Heck hydroarylation of unactivated alkenes has emerged as an essential reaction for regioselective hydroarylation. Herein, we report a palladium-catalyzed reductive Heck hydroarylation of unactivated alkenes under mild conditions with enhanced functional group tolerance using hydrosilane as the reducing reagent. Under the optimal conditions, the alkylarene yields increased, resulting in minimal undesired products.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2023
College of Chemistry and Chemical Engineering, Qingdao University, Ningxia Road 308#, Qingdao, 266071, China.
Transition-metal-catalyzed hydroarylation of unsymmetrical internal alkynes remains challenging because of the difficulty in controlling regioselectivity and stereoselectivity. Moreover, the enantioselective hydroarylation of alkynes using organoboron reagents has not been reported. Herein, we report for the first time that palladium compounds can catalyze the hydroarylation of 1-alkynylindoles with organoborons for the synthesis of chiral C-N atropisomers.
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