An efficient Pd-catalyzed C(sp)-H selective iodination of 8-methylquinolines is reported herein for the first time. Because of the versatility of organic iodides, the method offers a facile access to various C8-substituted quinolines. By slightly switching the reaction conditions, an efficient C(sp)-H acetoxylation of 8-methylquinolines has also been enabled. Both approaches feature mild reaction conditions, good tolerance of functional groups, and a broad substrate scope.
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http://dx.doi.org/10.1021/acs.joc.2c00076 | DOI Listing |
Molecules
September 2023
Laboratory of Industrial and Synthetic Organic Chemistry (LISOC), Department of Chemistry and Chemical Technologies, University of Calabria, Via Pietro Bucci 12/C, 87036 Arcavacata di Rende, Italy.
2-Propargyl-1,3-dicarbonyl compounds have been carbonylated under oxidative conditions and with the catalysis of the PdI/KI catalytic system to selectively afford previously unreported 2-(4-acylfuran-2-yl)acetamides in fair to good yields (54-81%) over 19 examples. The process takes place under relatively mild conditions and occurs via a mechanistic pathway involving C-H activation by oxidative monoamincarbonylation of the terminal triple bond of the substrates with formation of 2-ynamide intermediates, followed by 5---cyclization (via intramolecular conjugate addition of the in situ formed enolate to the 2-ynamide moiety) and aromative isomerization.
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