Intramolecular Arene C-H to C-P Functionalization Mediated by Ni(II) and Pd(II).
Intramolecular Arene C-H to C-P Functionalization Mediated by Ni(II) and Pd(II).
复制标题
Ni(II) 和 Pd(II) 介导的分子内芳烃 C-H 到 C-P 官能化。
DOI：
10.1021/om400424a
复制
发表时间：
2013
期刊：
影响因子：
2.8
通讯作者：
Agapie,Theodor
中科院分区：
文献类型：
--
作者：
Suseno,Sandy;Agapie,Theodor
采用具有三芳基苯骨架的三（膦）配体来支持单镍（II）和钯（II）配合物。两个膦臂与金属中心配位，而第三个膦臂与中心芳烃脱芳构化形成C-P键。去质子化影响中心环的rearomatization和金属还原从M（II）到M（0）。总转化对应于未活化的芳烃C-H键到C-P键的官能化。这种转变代表了一种罕见的C-H官能化机制，由第10族金属与芳烃π系统的相互作用促进。这种转换是让人想起，并扩大了最近报道的分子内重排的联芳基膦配体常见的第10组催化的范围。
A tris(phosphine) ligand with a triarylbenzene backbone was employed to support mono-nickel(II) and -palladium(II) complexes. Two phosphine arms coordinated to the metal center, while the third phosphine was found to form a C–P bond with dearomatization of the central arene. Deprotonation effected the rearomatization of the central ring and metal reduction from M(II) to M(0). The overall conversion corresponds to a functionalization of an unactivated arene C–H bond to a C–P bond. This transformation represents a rare type of mechanism of C–H functionalization, facilitated by the interactions of the group 10 metal with the arene π system. This conversion is reminiscent of and expands the scope of recently reported intramolecular rearrangements of biaryl phosphine ligands common in group 10 catalysis.