N,N-Diethyl O-Carbamate: Directed Metalation Group and Orthogonal Suzuki-Miyaura Cross-Coupling Partner
N,N-Diethyl O-Carbamate: Directed Metalation Group and Orthogonal Suzuki-Miyaura Cross-Coupling Partner
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DOI：
10.1021/ja907700e
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发表时间：
2009-12-16
影响因子：
15
通讯作者：
Snieckus, Victor
中科院分区：
文献类型：
--
作者：
Antoft-Finch, Aurora;Blackburn, Tom;Snieckus, Victor
使用廉价、实验室稳定的催化剂 NiCl2(PCy3)2 描述了芳基 O-氨基甲酸酯的第一个 Suzuki−Miyaura 交叉偶联，芳基 O-氨基甲酸酯是定向邻位金属化 (DoM) 化学中一种多功能且强大的定向金属化基团 (DMG)。芳基和杂芳基O-氨基甲酸酯具有广泛的合成范围和良好的效率。水的作用以及游离硼酸和环硼氧烷之间的水解平衡被确定为该转化的关键参数。当与DoM和传统的Pd催化的Suzuki-Miyaura策略相结合时，该方法为独特取代的分子提供了简洁的路线，避免了苯酚的保护/脱保护和使用强亲核交叉偶联伙伴的需要。
The first Suzuki−Miyaura cross-coupling of an arylO-carbamate, a versatile and powerful directed metalation group (DMG) in directed ortho metalation (DoM) chemistry, is described using the inexpensive, bench-stable catalyst NiCl2(PCy3)2. Broad synthetic scope and good efficiency are demonstrated for aryl and heteroarylO-carbamates. The role of water and hydrolysis equilibrium between free boronic acid and boroxine was established to be a crucial parameter for this transformation. When combined with DoM and traditional Pd-catalyzed Suzuki−Miyaura strategies, the methodology offers concise routes to uniquely substituted molecules, avoiding the need for protection/deprotection of the phenol and the use of strongly nucleophilic cross-coupling partners.