An efficient, tandem one-pot approach to synthesize multisubstituted 2-acylpyrroles from readily prepared -tosyl triazoles and 2-hydroxymethylallyl carbonates is reported. The reaction proceeds via Rh(II)-catalyzed O-H insertion, [3,3]-sigmatropic rearrangement, Pd(0)-catalyzed oxidative addition, intramolecular cyclization, DBU-promoted E1cB elimination, double bond isomerization, and aromatization, enabling the disconnection and formation of multiple bonds in one reactor. The approach represents a highly regioselective way to access di-, tri-, and tetra-substituted H pyrroles with high efficiency.
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http://dx.doi.org/10.1021/acs.joc.2c02602 | DOI Listing |
Org Biomol Chem
December 2023
Department of Chemistry (BK21 Four), Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, Korea.
Transition metal-catalyzed dipolar cycloaddition is one of the most efficient and powerful synthetic strategies to produce diverse heterocycles. In particular, for the construction of oxygen-containing heterocycles, which are valuable structural motifs found in pharmaceuticals and natural compounds, transition metal-catalyzed oxa-dipolar cycloaddition using an oxygen-containing dipole has emerged as a promising method. In recent years, the 1,4-O/C dipole synthons 2-alkylidenetrimethylene carbonate and 2-hydroxymethylallyl carbonate have been developed and successfully applied to palladium-catalyzed oxa-[4 + ] dipolar cycloadditions with diverse dipolarophiles.
View Article and Find Full Text PDFJ Org Chem
January 2023
Department of Chemistry (BK21 Four), Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, Korea.
An efficient, tandem one-pot approach to synthesize multisubstituted 2-acylpyrroles from readily prepared -tosyl triazoles and 2-hydroxymethylallyl carbonates is reported. The reaction proceeds via Rh(II)-catalyzed O-H insertion, [3,3]-sigmatropic rearrangement, Pd(0)-catalyzed oxidative addition, intramolecular cyclization, DBU-promoted E1cB elimination, double bond isomerization, and aromatization, enabling the disconnection and formation of multiple bonds in one reactor. The approach represents a highly regioselective way to access di-, tri-, and tetra-substituted H pyrroles with high efficiency.
View Article and Find Full Text PDFOrg Lett
September 2022
Department of Chemistry (BK21 Four), Research Institute of Natural Science, Gyeongsang National University, 52828 Jinju, Korea.
Dual Rh(II)/Pd(0) relay catalysis of -sulfonyl triazoles and 2-hydroxymethylallyl carbonates has been developed, which affords -sulfonyl pyrrolidines in moderate to good yields with high diastereoselectivities. The reaction proceeds via a relay mechanism involving O-H insertion onto the α-imino Rh(II)-carbene, [3,3]-sigmatropic rearrangement, dipole formation through Pd(0)-catalyzed decarboxylation, and intramolecular -allylation, leading to the formation of multiple bonds in a one-pot operation.
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