Ir-catalyzed borylation of 2-substituted indoles selectively yields 7-borylated products in good yields. N-Protection, required for previous functionalizations of 2-substituted indoles, is unnecessary.
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http://dx.doi.org/10.1021/ja0631652 | DOI Listing |
Asian J Org Chem
January 2025
Department of Medicinal Chemistry, Ernest Mario School of Pharmacy, Rutgers, The State University of New Jersey, 160 Frelinghuysen Road, Piscataway, New Jersey 08854, USA.
A one-pot process was developed to synthesize in moderate to high yield a series of 2-substituted indoles and 7-azaindoles starting from 2-iodo--mesylarylamines and terminal alkynes in the presence of CuO in DMF at 90-120 °C. Without isolation of any intermediate, our optimized conditions enabled the introduction of ester, phenyl, hydroxymethyl, hydroxyethyl, -Boc-aminomethyl, and methyl at the 2-postion of indoles and 7-azaindoles. The reaction tolerates a variety of substrates containing halogens, or acid- or base-sensitive functional groups without requiring a Pd catalyst, a ligand, or a base.
View Article and Find Full Text PDFACS Omega
October 2024
Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia.
Cancer is a complex disease driven by the dysregulation of multiple signaling pathways and cellular processes. The development of compounds capable of exerting multitarget actions against these key pathways involved in cancer progression is a promising therapeutic approach. Here, a series of novel (/)--(4-(2-(2-(substituted)hydrazineyl)-2-oxoethyl)thiazol-2-yl)-1-indole-2-carboxamide derivatives (-) were designed, synthesized, and evaluated for their biological activity.
View Article and Find Full Text PDFJ Org Chem
October 2024
Department of Chemistry and Biochemistry, Texas State University, 601 University Dr., San Marcos, Texas 78666, United States.
Herein, we describe a novel reaction between C-2-substituted indoles and 2-nitroacetophenones leading to a variety of indole-containing heterocyclic scaffolds. At 60 °C in AcOH with HSO as catalyst, C-2 aryl indoles give 3-(2-nitrovinyl)-indoles with high or geometric selectivity depending on the type of substrate utilized. These compounds undergo an electrocyclization process in a sealed vial in a microwave apparatus in DMF at 250 °C to give benzo[]carbazoles and naphtho[2,1-]carbazoles depending on whether the C-2 aromatic moiety is phenyl or naphthyl.
View Article and Find Full Text PDFJ Org Chem
August 2024
Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Recognition and Function, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
We present here a new method for the synthesis of 2-substituted-3-aryl benzoheterocycles through a more challenging constrained [1,5]-type Friedel-Crafts reaction/rearrangement and aromatization process. By using the readily available 2-aryoxy-1,3-indandiones and 2-arylamino-1,3-indandiones, a range of 2-substituted-3-aryl benzofurans and indoles were prepared in good to excellent yields (yields up to 86%) under the catalysis of CFSOH or Sm(OTf). Compared with previous methods for constructing similar structures, this approach offers several advantages, including the use of easily accessible starting materials, mild reaction conditions, high yield, excellent regio- and diastereoselectivity, and a broad substrate scope.
View Article and Find Full Text PDFThis study showcases the 1,2-migration reactions of alkyl and aryl groups on the indole molecule. Trifluoromethanesulfonic acid effectively facilitates the migration of the substituent from C3- to C2-position of the indole structure. The resulting C2-substituted indoles offer a valuable pathway for the synthesis of natural products and medicinal compounds.
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