Joseph Ebbin, Hernandez Rafael D, Tunge Jon A
Department of Chemistry, The University of Kansas, 1567 Irving Rd., Lawrence, KS 66045, USA.
Chemistry. 2023 Oct 18;29(58):e202302174. doi: 10.1002/chem.202302174. Epub 2023 Sep 7.
In recent years, there has been a concerted drive to develop methods that are greener and more sustainable. Being an earth-abundant transition metal, cobalt offers an attractive substitute for commonly employed precious metal catalysts, though reactions engaging cobalt are still less developed. Herein, we report a method to achieve the decarboxylative allylation of nitrophenyl alkanes, nitroalkanes, and ketones employing cobalt. The reaction allows for the formation of various substituted allylated products in moderate-excellent yields with a broad scope. Additionally, the synthetic potential of the methodology is demonstrated by the transformation of products into versatile heterocyclic motifs. Mechanistic studies revealed an in situ activation of the Co(II)/dppBz precatalyst by the carboxylate salt to generate a Co(I)-species, which is presumed to be the active catalyst.
近年来，人们一直在齐心协力地开发更绿色、更可持续的方法。钴作为一种储量丰富的过渡金属，为常用的贵金属催化剂提供了一种有吸引力的替代品，不过涉及钴的反应仍不太成熟。在此，我们报道了一种使用钴实现硝基苯基烷烃、硝基烷烃和酮的脱羧烯丙基化反应的方法。该反应能够以中等至优异的产率形成各种取代的烯丙基化产物，适用范围广泛。此外，该方法的合成潜力通过将产物转化为多功能杂环基序得到了证明。机理研究表明，羧酸盐原位活化Co(II)/dppBz预催化剂生成Co(I)物种，该物种被认为是活性催化剂。
