Reaction of Nitrogen-Radicals with Organometallics Under Ni-Catalysis: N-Arylations and Amino-Functionalization Cascades
Reaction of Nitrogen-Radicals with Organometallics Under Ni-Catalysis: N-Arylations and Amino-Functionalization Cascades
复制标题
Ni 催化下氮自由基与有机金属的反应：N-芳基化和氨基官能化级联
DOI：
10.1002/ange.201900510
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发表时间：
2019
影响因子：
--
通讯作者：
Angelini L
中科院分区：
文献类型：
--
作者：
Angelini L
在此，我们报告了一种通过有机基-NiI物种的基态单电子转移产生氮自由基的策略。根据 N-自由基的亲和性，已经开发了两种类型的工艺。在亲核氨基自由基的情况下，可实现与芳基有机锌、有机硼和有机硅试剂的直接N-芳基化。对于亲电酰胺基自由基，已经开发了涉及分子内环化，然后与芳基和烷基有机金属反应的级联过程。 N-环化-烷基化级联引入了一种新颖的逆向合成断开方法，用于组装取代的内酰胺和吡咯烷，其潜力在四种毒液生物碱的简短全合成中得到了证明。
Herein, we report a strategy for the generation of nitrogen‐radicals by ground‐state single electron transfer with organyl–NiIspecies. Depending on the philicity of the N‐radical, two types of processes have been developed. In the case of nucleophilic aminyl radicals direct N‐arylation with aryl organozinc, organoboron, and organosilicon reagents was achieved. In the case of electrophilic amidyl radicals, cascade processes involving intramolecular cyclization, followed by reaction with both aryl and alkyl organometallics have been developed. The N‐cyclization–alkylation cascade introduces a novel retrosynthetic disconnection for the assembly of substituted lactams and pyrrolidines with its potential demonstrated in the short total synthesis of four venom alkaloids.