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<p>General methods for the highly site-selective monocoupling of alkyl 2,4- and 2,5-dihalobenzoates have been discovered. By switching from PdCl<sub>2</sub>(PCy<sub>3</sub>)<sub>2</sub>/P(<i>p</i>-MeOPh)<sub>3</sub> to Pd(OAc)<sub>2</sub>/<b>L9</b>, the preferred coupling site can be shifted from the C2-position to the C4 or C5-position. The formation of the substituted alkyl monohalobenzoate derivatives is highly site-selective and tolerant to both electron-withdrawing and electron-donating groups on aryl and heteroaryl titanium reagents and the reaction gives twenty-four substituted alkyl monohalobenzoate derivatives (except for <b>4ea</b>, the other were novel compounds) were prepared and their structure was confirmed by FTIR, spectroscopy, <sup>1</sup>H and <sup>13</sup>C NMR, and mass spectrometry. This simple synthetic route is designed to improve the rapid construction of mutiple aryl cross-coupling products.</p> Graphical abstract <p>The same substrate alkyl 2,4- and 2,5-dihalobenzoates can selectively generate C2-position and C4- or C5-position products by switching catalytic system from PdCl<sub>2</sub>(PCy<sub>3</sub>)<sub>2</sub>/P(<i>p</i>-MeOPh)<sub>3</sub> to Pd(OAc)<sub>2</sub>/<b>L9</b>. The reaction gives twentyfour substituted alkyl monohalobenzoate derivatives, and the simple synthetic route is designed to improve the rapid construction of mutiplearyl cross-coupling products.</p>

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Palladium-catalyzed site-selective arylation of alkyl 2,4- and 2,5-dihalobenzoates with aryl titanium reagents

  • 期刊论文

  • 发表日期：

    2025年7月5日

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  • Jing Lv

摘要

General methods for the highly site-selective monocoupling of alkyl 2,4- and 2,5-dihalobenzoates have been discovered. By switching from PdCl2(PCy3)2/P(p-MeOPh)3 to Pd(OAc)2/L9, the preferred coupling site can be shifted from the C2-position to the C4 or C5-position. The formation of the substituted alkyl monohalobenzoate derivatives is highly site-selective and tolerant to both electron-withdrawing and electron-donating groups on aryl and heteroaryl titanium reagents and the reaction gives twenty-four substituted alkyl monohalobenzoate derivatives (except for 4ea, the other were novel compounds) were prepared and their structure was confirmed by FTIR, spectroscopy, 1H and 13C NMR, and mass spectrometry. This simple synthetic route is designed to improve the rapid construction of mutiple aryl cross-coupling products.

Graphical abstract

The same substrate alkyl 2,4- and 2,5-dihalobenzoates can selectively generate C2-position and C4- or C5-position products by switching catalytic system from PdCl2(PCy3)2/P(p-MeOPh)3 to Pd(OAc)2/L9. The reaction gives twentyfour substituted alkyl monohalobenzoate derivatives, and the simple synthetic route is designed to improve the rapid construction of mutiplearyl cross-coupling products.