Rhodium-Catalyzed Borylation of Aryl 2-Pyridyl Ethers through Cleavage of the Carbon-Oxygen Bond: Borylative Removal of the Directing Group
Rhodium-Catalyzed Borylation of Aryl 2-Pyridyl Ethers through Cleavage of the Carbon-Oxygen Bond: Borylative Removal of the Directing Group
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DOI：
10.1021/ja511622e
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发表时间：
2015-02-04
影响因子：
15
通讯作者：
Chatani, Naoto
中科院分区：
文献类型：
--
作者：
Kinuta, Hirotaka;Tobisu, Mamoru;Chatani, Naoto
在铑的催化下，芳基2-吡啶醚与二硼试剂反应，通过C(芳基)-O键的活化生成芳基硼酸衍生物。1，2-二取代芳烃的直接合成是通过2-吡啶氧基的催化邻位C-H键官能化，然后用硼基取代该基团来实现的。几个对照实验表明，底物2-位的sp2氮原子的存在和硼基试剂的使用对于芳基2-吡啶醚中相对惰性的C(芳基)-O键的活化至关重要。
The rhodium-catalyzed reaction of aryl 2-pyridyl ethers with a diboron reagent results in the formation of arylboronic acid derivatives via activation of the C(aryl)-O bonds. The straightforward synthesis of 1,2-disubstituted arenes was enabled through catalytic ortho C-H bond functionalization directed by the 2-pyridyloxy group followed by substitution of this group with a boryl group. Several control experiments revealed that the presence of a sp2 nitrogen atom at the 2-position of the substrate and the use of a boron-based reagent were crucial for the activation of the relatively inert C(aryl)-O bond of aryl 2-pyridyl ethers.