In sharp contrast to the well researched and well developed aminocarbonylation of alkenes,the dearomative carbamoylation of abundant areneπ-systems has scarcely been studied despite its great potential to enrich the ...In sharp contrast to the well researched and well developed aminocarbonylation of alkenes,the dearomative carbamoylation of abundant areneπ-systems has scarcely been studied despite its great potential to enrich the diversity-oriented synthesis of high-value amides.The formidable challenges associated with such dearomatization include the low reactivity of stable aromaticπ-systems and intricate selectivity issues.Herein,we disclose a general approach toward highly selective dearomative carbamoylations of areneπ-bonds under CO-gas-free conditions.Its extraordinary versatility was demonstrated by tolerating a broad range of nucleophilic partners with high yields and excellent selectivities,thus providing modular access to the divergent synthesis ofβ-functionalized primary amides.In addition,diverse downstream derivatizations including a formal C–H 1,2-olefination/carbamoylation reaction were conducted,exhibiting great potential in synthetic and medicinal chemistry.展开更多
基金the National Natural Science Foundation of China(grant no.22271251)the Fundamental Research Funds for the Central Universities(grant nos.226-2023-00016,226-2023-00115,and 226-2022-00224).
文摘In sharp contrast to the well researched and well developed aminocarbonylation of alkenes,the dearomative carbamoylation of abundant areneπ-systems has scarcely been studied despite its great potential to enrich the diversity-oriented synthesis of high-value amides.The formidable challenges associated with such dearomatization include the low reactivity of stable aromaticπ-systems and intricate selectivity issues.Herein,we disclose a general approach toward highly selective dearomative carbamoylations of areneπ-bonds under CO-gas-free conditions.Its extraordinary versatility was demonstrated by tolerating a broad range of nucleophilic partners with high yields and excellent selectivities,thus providing modular access to the divergent synthesis ofβ-functionalized primary amides.In addition,diverse downstream derivatizations including a formal C–H 1,2-olefination/carbamoylation reaction were conducted,exhibiting great potential in synthetic and medicinal chemistry.
