Palladium-Catalyzed Picolinamide-Directed Acetoxylation of Unactivated γ-C(sp3)-H Bonds of Alkylamines
Palladium-Catalyzed Picolinamide-Directed Acetoxylation of Unactivated γ-C(sp3)-H Bonds of Alkylamines
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DOI：
10.1002/adsc.201400121
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发表时间：
2014-05-05
影响因子：
5.4
通讯作者：
Chen, Gong
中科院分区：
文献类型：
--
作者：
Li, Qiong;Zhang, Shu-Yu;Chen, Gong
我们报道了一种新的方案，钯催化n -烷基吡啶酰胺底物的- (sp(3))H键乙酰氧基化使用PhI(OAc)(2)氧化剂。这些反应涉及使用亚化学计量量的Li2CO3添加剂，它有效地抑制了竞争的分子内CH胺化过程。在此条件下，含取代基的n -丙基吡啶酰胺可以以优异的收率干净地转化为-乙酰氧基化胺产品。这种CH乙酰氧基化也可以与其他pd催化的吡啶酰胺导向的CH功能化反应协同使用，以实现支架的快速多样化。
We report a new protocol for palladium-catalyzed acetoxylation of the -C(sp(3))H bonds of N-alkylpicolinamide substrates using PhI(OAc)(2) oxidant. These reactions involve the use of substoichiometric amounts of Li2CO3 additive, which effectively suppresses the competing intramolecular CH amination process. Under these conditions, N-propylpicolinamides bearing substituents can be cleanly converted to -acetoxylated amine products in excellent yield. This CH acetoxylation can also be used in concert with other Pd-catalyzed picolinamide-directed CH functionalization reactions for rapid scaffold diversification.