Synthesis of Ti Complexes Supported by an ortho-terphenoxide Ligand and their Applications in Alkyne Hydroamination Catalysis.
Synthesis of Ti Complexes Supported by an ortho-terphenoxide Ligand and their Applications in Alkyne Hydroamination Catalysis.
复制标题
邻三苯酚配体负载的钛配合物的合成及其在炔烃氢氨化催化中的应用。
DOI：
10.1021/acs.organomet.2c00593
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发表时间：
2023
期刊：
影响因子：
2.8
通讯作者：
Tonks,IanA
中科院分区：
文献类型：
--
作者：
Butler,StevenK;Ashbrook,EthanP;Tonks,IanA
报道了一系列芳基连接双酚氧配体3，3″-di-tert-butyl-5，5″-dimethyl-[1，1′：2′，1″-terphenyl]-2，2″-bis(olate)，(TPO)H_2的钛配合物的合成。这种邻位连接的三苯基配体建立在先前报道的间位和对位连接的三苯基配体的基础上，完成了三苯氧基配体的异构体系列。四配位(TPO)Ti(NMe2)2是一种与多种芳胺反应的活性催化剂，在与不对称的炔烃反应中表现出良好的区域选择性。末端炔烃，如苯乙炔，与关键的氮杂环丁烯中间体发生额外的插入反应，进一步证明芳氧钛配合物容易发生这种进一步的反应。
The synthesis of a series of Ti complexes of an aryl-linkedbis-phenoxide ligand, 3,3″-di-tert-butyl-5,5″-dimethyl-[1,1′:2′,1″-terphenyl]-2,2″-bis(olate), (TPO)H2, is reported. This ortho-linked terphenyl ligand builds on previously reported meta- and para-linked terphenyl-based ligands, completing the isomeric series of terphenoxide ligands. The 4-coordinate (TPO)Ti(NMe2)2is an active catalyst for alkyne hydroamination with a variety of arylamines, revealing good regioselectivity in reactions with unsymmetric alkynes. Terminal alkynes such as phenylacetylene undergo additional insertion reactions with the key azatitanacyclobutene intermediates, providing further evidence that Ti aryloxide complexes are susceptible to this further reactivity.