Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada.
J Am Chem Soc. 2009 Dec 16;131(49):17750-2. doi: 10.1021/ja907700e.
The first Suzuki-Miyaura cross-coupling of an aryl O-carbamate, a versatile and powerful directed metalation group (DMG) in directed ortho metalation (DoM) chemistry, is described using the inexpensive, bench-stable catalyst NiCl(2)(PCy(3))(2). Broad synthetic scope and good efficiency are demonstrated for aryl and heteroaryl O-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.
首次报道了芳基 O-氨基甲酸酯的 Suzuki-Miyaura 交叉偶联反应，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、强大的导向金属化基团（DMG），使用廉价、稳定的催化剂 NiCl(2)(PCy(3))(2) 实现了这一转化。该反应对芳基和杂芳基 O-氨基甲酸酯具有广泛的合成适用性和良好的效率。确定了水和游离硼酸与硼酸酯之间的水解平衡在该转化中的关键作用。当与 DoM 和传统的 Pd 催化的 Suzuki-Miyaura 策略相结合时，该方法为独特取代分子提供了简洁的路线，避免了酚的保护/脱保护以及使用强亲核性交叉偶联试剂的需要。
