Manganese(I) Catalyzed ortho C-H Allylation of Benzoic Acids.
Manganese(I) Catalyzed ortho C-H Allylation of Benzoic Acids.
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锰 (I) 催化苯甲酸的邻位 C-H 烯丙基化。
DOI：
10.1002/anie.202301839
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发表时间：
2023
影响因子：
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通讯作者：
L. Goossen
中科院分区：
文献类型：
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作者：
J. Goebel;J. Stemmer;Florian Belitz;L. Goossen
发现3d-金属催化剂Mn（CO）5 Br在新亚铜灵作为配体的存在下有效地促进芳烃羧酸酯的邻位C-H烯丙基化。尽管导向基团和催化剂体系简单，但选择性远远超过现有技术，因为单烯丙基化产物仅以最小受阻邻位的高选择性获得。导向基团可以任选地通过原位脱羧除去，从而打开烯丙基芳烃的区域选择性进入。该方法的制备实用性及其与其他方法的正交性通过44种具有其他难以获得的取代模式的产物（包括3-溴烯丙基苯、3-烯丙基苯并呋喃或5-烯丙基-2-甲基硝基苯）来证明。
The 3d-metal catalyst Mn(CO)5Br was found to efficiently promote ortho C-H allylations of arenecarboxylates in the presence of neocuproine as the ligand. Despite the simplicity of directing group and catalyst system, the selectivity goes well beyond the state of the art in that mono-allylated products are obtained exclusively with high selectivities for the least hindered ortho-position. The directing group can optionally be removed by in situ decarboxylation, opening up a regioselective entry to allyl arenes. The preparative utility of the process and its othogonality to other approaches was demonstrated by 44 products with otherwise hard-to-access substitution patterns, including 3-bromo-allylbenzene, 3-allylbenzofuran, or 5-allyl-2-methylnitrobenzene.