Methods for the modification of indole derivatives are powerful techniques in organic, medicinal, and biomolecular chemistry. Here, we report a protocol for the C-H alkenylation of N-H indoles with β-chlorovinyl dithianes to furnish alkenyl indoles through dual 1,3-sulfur rearrangements. This alkenylation protocol could selectively prepare a variety of vinyl indoles in moderate to high yields with excellent functional group tolerance.
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http://dx.doi.org/10.1021/acs.orglett.2c03052 | DOI Listing |
Org Biomol Chem
January 2025
College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang, 473061, P. R. China.
A highly practical and efficient Cp*Co(III)-catalyzed C-H alkylation/alkenylation reaction of anilides with maleimides and acrylates was developed, during which a weakly coordinating amide carbonyl group functioned as the directing group. This approach features high efficiency, good functional group tolerance, and broad substrate scope, and a variety of 3-substituted succinimides and -alkenylated anilides were synthesized in moderate to excellent yields. Furthermore, the reaction is highly selective, affording mono--alkylated/alkenylated products only.
View Article and Find Full Text PDFJ Org Chem
January 2025
Collaborative Innovation Center for Advanced Organic Chemical Materials Co-Constructed by the Province and Ministry, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, Hubei Key Laboratory for Precision Synthesis of Small Molecule Pharmaceuticals, College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, P. R. China.
Direct functionalization of native (N-H) indoles via C-H activation remains a challenge. Herein, we report a salicylaldehyde-promoted cobalt-catalyzed selective C2-H Heck reaction of native (N-H) indoles with both active and unactivated olefins in the presence of free N-H bonds. A series of structurally diverse C2-alkenylated native (N-H) indoles including natural product and drug derivatives were prepared directly and effectively without additional preprotection and deprotection procedures.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry, Malaviya National Institute of Technology Jaipur, Jaipur 302017, Rajasthan, India.
J Org Chem
January 2025
Collaborative Innovation Center for Advanced Organic Chemical Materials Co-constructed by the Province and Ministry, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules. Hubei Key Laboratory for Precision Synthesis of Small Molecule Pharmaceuticals. College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, P. R. China.
A ligand-promoted oxidative dehydrogenation C-H alkenylation of indoles and olefins was achieved using commercial and low-cost Co(NO)·6HO as a catalyst and Mn(OAc) as an oxidant. The design and selection of electrically unique methyl-substituted salicylaldehyde as a ligand is the key to achieve this transformation. This protocol can introduce an indole backbone into diverse bioactive molecules such as ibuprofen, naproxen, and Estrol for late-stage synthetic modification, which has potential applications in the discovery of drug molecules containing an indole motif.
View Article and Find Full Text PDFJ Org Chem
January 2025
Jiangsu Key Laboratory for Chemistry of Low Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian 223300, China.
An unprecedented Pd-catalyzed cascade alkyne insertion/Heck/C-H activation reaction of -iodophenyl alkenyl ethers and diarylacetylenes has been developed. Diversified tetracyclic-fused dihydroindeno[2,1-]chromenes bearing a quaternary center were constructed in an efficient, straightforward, and atom-economic way with good to excellent yields. The protocol features high bonding efficiency, operational simplicity, broad substrate scope, and easy scale-up.
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