Constructing a Catalytic Cycle for C-F to C-X (X = O, S, N) Bond Transformation Based on Gold-Mediated Ligand Nucleophilic Attack

被引:25
|
作者
Hu, Ji-Yun [1 ]
Zhang, Jing [2 ]
Wang, Gao-Xiang [1 ]
Sun, Hao-Ling [3 ,4 ]
Zhang, Jun-Long [1 ]
机构
[1] Peking Univ, Coll Chem & Mol Engn, State Key Lab Rare Earth Mat Chem & Applicat, Beijing Natl Lab Mol Sci, Beijing 100871, Peoples R China
[2] Chinese Acad Sci, Grad Univ, Coll Mat Sci & Optoelect Technol, Beijing 100049, Peoples R China
[3] Beijing Normal Univ, Dept Chem, Beijing 100875, Peoples R China
[4] Beijing Normal Univ, Beijing Key Lab Energy Convers & Storage Mat, Beijing 100875, Peoples R China
关键词
CARBON-FLUORINE BONDS; OXIDATIVE ADDITION; ACTIVATION REACTIONS; PI INTERACTION; HYDRODEFLUORINATION; COMPLEXES; REACTIVITY; ARYL; PENTAFLUOROPYRIDINE; COBALT;
D O I
10.1021/acs.inorgchem.5b02634
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A tricoordinated gold(I) chloride complex, tBuXantphosAuCl, supported by a sterically bulky 9,9-dimethyl-4,5-bis(di-tert-butylphosphino)xanthene ligand (tBuXantphos) was synthesized. This complex features a remarkably longer Au-Cl bond length [2.632(1) angstrom] than bicoordinated linear gold complexes (2.27-2.30 angstrom) and tricoordinated XantphosAuCl [2.462(1) angstrom]. Single-crystal X-ray diffraction analysis of a cocrystal of tBuXantphosAuCl and pentafluoronitrobenzene (PFNB) and UV-vis spectroscopic titration experiments revealed the existence of an anion-pi interaction between the Cl anion ligand and PFNB. Stoichiometric reaction between PFNB and tBuXantphosAuOtBu, after replacement of Cl by a more nucleophilic tBuO anion ligand, showed higher reactivity and para selectivity in the transformation of C-F to C-OtBu bond, distinctively different from that when only KOtBu was used (ortho selectivity) under the identical condition. Mechanistic studies including density functional theory calculations suggested a gold-mediated nucleophilic ligand attack of the C-F bond pathway via an SNAr process. On the basis of these results, using trimethylsilyl derivatives TMS-X (X = OMe, SEt, NEt2) as the nucleophilic ligand source and the fluorine acceptor, catalytic transformation of the C-F bond of aromatic substrates to the C-X (X = O, S, N) bond was achieved with tBuXantphosAuCl as the catalyst (up to 20 turnover numbers).
引用
收藏
页码:2274 / 2283
页数:10
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