Saint Petersburg State University , Institute of Chemistry , 7/9 Universitetskaya nab. , St. Petersburg 199034 , Russia.
J Org Chem. 2019 Sep 6;84(17):11275-11285. doi: 10.1021/acs.joc.9b01634. Epub 2019 Aug 20.
The synthesis of methyl 5-aminopyrrole-3-carboxylates from 4-methyleneisoxazol-5-ones via "cyanide Michael addition/methylation/reductive isoxazole-pyrrole transformation" is developed. The last step occurs in a domino mode involving Mo(CO)-mediated reductive isoxazole ring-opening, Mo(CO)-catalyzed --isomerization of the enamine intermediate followed by 1,5-- cyclization. 5-Amino-1-pyrrolo-3-carboxylates react with 1,3-diketones, affording pyrrolo[1,2-]pyrimidine-7-carboxylates, and are easily converted into 2-diazo-2-pyrrole-4-carboxylates. These compounds demonstrate the reactivity of both diazo compounds, giving pyrrole-containing products of intra/intermolecular azo coupling, and carbenes to give pyrrole-containing insertion products into CH and OH bonds under photolysis.
通过“氰化物迈克尔加成/甲基化/还原异恶唑-吡咯转化”，从 4-亚甲基异恶唑-5-酮合成 5-氨基吡咯-3-羧酸甲酯。最后一步以多羰基钼（Mo(CO)）介导的还原异恶唑开环、烯胺中间体的 Mo(CO)催化--异构化和 1,5--环化为多米诺模式发生。5-氨基-1-吡咯并[1,2-]嘧啶-7-羧酸酯与 1,3-二酮反应，生成吡咯并[1,2-]嘧啶-7-羧酸酯，并且容易转化为 2-重氮-2-吡咯-4-羧酸酯。这些化合物展示了重氮化合物的反应性，在光解下，通过分子内/分子间偶氮耦合生成含吡咯的产物，通过碳烯插入 CH 和 OH 键生成含吡咯的产物。
