School of Chemistry, University of Bristol, Bristol, BS8 1TS, United Kingdom.
Department of Medicinal Chemistry, Research and Early Development, Respiratory and Immunology, BioPharmaceuticals R&D, AstraZeneca, SE 43183 Mölndal, Sweden.
J Am Chem Soc. 2021 Sep 29;143(38):15593-15598. doi: 10.1021/jacs.1c08615. Epub 2021 Sep 21.
Structurally complex benzo- and spiro-fused N-polyheterocycles can be accessed via intramolecular Pd(0)-catalyzed alkene 1,2-aminoarylation reactions. The method uses -(pentafluorobenzoyloxy)carbamates as the initiating motif, and this allows aza-Heck-type alkene amino-palladation in advance of C-H palladation of the aromatic component. The chemistry is showcased in the first total synthesis of the complex alkaloid (+)-pileamartine A, which has resulted in the reassignment of its absolute stereochemistry.
通过分子内 Pd(0)催化的烯烃 1,2-氨基芳基化反应，可以得到结构复杂的苯并和螺稠合 N-多杂环。该方法使用 -(五氟苯甲酰氧基)氨基甲酸酯作为引发基，这使得在芳环组分的 C-H 钯化之前，可以进行氮杂-Heck 型烯烃氨基钯化。该反应在复杂生物碱 (+)-pileamartine A 的首次全合成中得到了应用，这导致其绝对立体化学的重新分配。
