We report a new application of -amino-7-azaindole as a new bidentate-directing group for [Ru(-cymene)Cl]-catalyzed C(sp)-H alkenylation/annulation of -(1-pyrrolo[2,3-]pyridin-1-yl)benzamides with internal alkynes to afford -isoquinolono-7-azaindole via the formation of C-C and C-N bonds. The reaction shows a wide range of substrate scope with different symmetrical and unsymmetrical alkynes, affording the desired product in good to excellent yields. In the case of unsymmetrical alkynes, a highly regioselective product was obtained, which was confirmed by single-crystal X-ray crystallography. A new ruthenium-4-methyl--(1-pyrrolo[2,3-]pyridin-1-yl)benzamide complex was isolated, and its structure was confirmed by single-crystal X-ray crystallography.
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http://dx.doi.org/10.1021/acs.joc.9b01598 | DOI Listing |
J Phys Chem A
January 2025
Department of Mechanical Engineering, The Hong Kong Polytechnic University, Kowloon, Hong Kong SAR 999077, China.
An adequate understanding of the NO interacting chemistry is a prerequisite for a smoother transition to carbon-lean and carbon-free fuels such as ammonia and hydrogen. In this regard, this study presents a comprehensive study on the H atom abstraction by NO from C to C alkynes, dienes, and trienes forming 3 HNO isomers (i.e.
View Article and Find Full Text PDFJ Org Chem
January 2025
State Key Laboratory of Antiviral Drugs, Pingyuan Laboratory, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, Henan, China.
A palladium-catalyzed [2 + 2 + 2] cyclization of 1,6-enynes with unsymmetrical alkynes has been successfully accomplished, resulting in the formation of a series of fused tricyclic hydronaphthofurans with high stereo- and regioselectivity in a single step. This reaction demonstrates 100% atomic economy and exhibits a broad substrate scope.
View Article and Find Full Text PDFChemistry
December 2024
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China.
Pd-catalyzed alkoxycarbonylation of internal alkynes provides a straightforward access to α,β-disubstituted acrylic esters. Compared with the well-established regioselective alkoxycarbonylation of terminal alkynes, the regioselective hydrocarboxylation of non-functionalized unsymmetric internal alkynes was more challenging owing to the delicate differences of properties between the two substituents. Herein, by using either monophosphine ligand based on 2,3-dihydrobenzo[d][1,3]oxaphosphole motif or bidentate ligand Ph-Phox, the regioselective alkoxycarbonylations of aryl-aryl, aryl-alkyl and alkyl-alkyl disubstituted alkynes were achieved, giving a diversity of trisubstituted α,β-unsaturated carboxylic esters with moderate to excellent yields and high regioselectivity.
View Article and Find Full Text PDFOrg Lett
November 2024
School of Chemistry, College of Science, University of Tehran, 14155-6455 Tehran, Iran.
Here we report a simultaneous construction of two C-C and two C-N bonds in a unified procedure that incorporates alkynoic acid trifunctionalization, ortho C-H functionalization, and amination cascade. In an ordered process, the regioselective alkyne insertion reaction is favored over the decarboxylation process. The presence of the carboxyl group in alkynoic acid ensures the high regioselectivity in the carbopalladation process, paving the way for a novel method to synthesize unsymmetrically 2,3-diaryl substituted indole scaffolds with excellent regioselectivity.
View Article and Find Full Text PDFJ Org Chem
November 2024
Department of Organic Chemistry, University of Madras, Guindy Campus, Chennai, Tamilnadu 600025, India.
A new palladium-catalyzed efficient method for the synthesis of substituted 9,10-phenanthrenes from 2-biaryl triflates with alkynes has been developed. This method provides a great opportunity to prepare various symmetrical and unsymmetrical phenanthrene derivatives in good yields. This reaction proceeds via C-OTf bond cleavage and alkyne insertion followed by C-H annulation.
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