Defluorinative Functionalization of Pd(II) Fluoroalkyl Complexes
Defluorinative Functionalization of Pd(II) Fluoroalkyl Complexes
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DOI：
10.1021/jacs.0c09505
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发表时间：
2020-10-28
影响因子：
15
通讯作者：
Szymczak, Nathaniel K.
中科院分区：
文献类型：
--
作者：
Wolfe, Michael M. Wade;Shanahan, James P.;Szymczak, Nathaniel K.
当受到芳基硼烷，阴离子三氟甲基和二氟苄基钯（II）配合物进行氟化物提取，然后由1，1-迁移插入。可以诱导所得中间体氟烷基物质经历随后的金属转移和从原位形成的氟硼酸酯（FB（Ar-3）（-））或外源硼酸/酯（ArB（OR）（2））和亲核活化剂的还原消除，代表净脱氟芳基化反应。后一种方法能够从分离的钯-CF 3络合物或Pd（PPh 3）（4）和其他市售试剂制备结构多样的底物范围。
When subjected to arylboranes, anionic trifluoromethyl and difluorobenzyl palladium(II) complexes undergo fluoride abstraction followed by 1,1-migratory insertion. The resulting intermediate fluoroalkyl species can be induced to undergo a subsequent transmetalation and reductive elimination from either an in situ formed fluoroboronate (FB(Ar-3)(-)) or an exogenous boronic acid/ ester (ArB(OR)(2)) and nucleophilic activator, representing a net defluorinative arylation reaction. The latter method enabled a structurally diverse substrate scope to be prepared from either an isolated palladium-CF3 complex, or from Pd(PPh3)(4) and other commercially available reagents.