Synthesis and Reactivity of the Fluoro Complex trans-[Pd(F)(4-C5NF4)(iPr2PCH2CH2OCH3)2]: C-F Bond Formation and Catalytic C-F Bond Activation Reactions

被引：67
作者：
Breyer, David [1 ]
Braun, Thomas [1 ]
Klaering, Paul [1 ]
机构：
[1] Humboldt Univ, Dept Chem, D-12489 Berlin, Germany
来源：
ORGANOMETALLICS | 2012年 / 31卷 / 04期
关键词：
CROSS-COUPLING REACTIONS; ELECTRON-DEFICIENT POLYFLUOROARENES; ENANTIOSELECTIVE FLUORINATION; ARYL FLUORIDES; OXIDATIVE-ADDITION; DIRECT ARYLATION; POLYFLUORINATED ARENES; REDUCTIVE ELIMINATION; ARYLBORONIC ACIDS; GRIGNARD-REAGENTS;
D O I：
10.1021/om200998d
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The reaction of [Pd(Me)(2)(tmeda)] (tmeda = N,N,N',N'-tetramethylethylendiamine) with the phosphine (Pr2PCH2CH2OCH3)-Pr-i resulted in the formation of the palladium(0) complex [Pd(Pr2PCH2CH2OCH3)(2)] (1). Treatment of 1 with pentafluoropyridine at room temperature yielded the C-F activation product trans-[Pd(F)(4-C5NF4)-((Pr2PCH2CH2OCH3)-Pr-i)(2)] (2). The triflato and bromo complexes trans-[Pd(OTf)(4-C5NF4)((Pr2PCH2CH2OCH3)-Pr-i)(2)] (4) and trans-[Pd(Br)(4-C5NF4)((Pr2PCH2CH2OCH3)-Pr-i)(2)] (5) could be prepared on reaction of complex 2 with EtOTf or 3-bromopropene, respectively. Treatment of 2 with Me3SiCl or HBpin (HBpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, pinacolborane) effects the formation of trans-[Pd(Cl)(4-C5NF4)((Pr2PCH2CH2OCH3)-Pr-i)(2)] (6) and trans-[Pd(H)(4-C5NF4)-((Pr2PCH)-Pr-i,CH2OCH3)(2)] (7). In catalytic experiments pentafluoropyridine could be converted into the 4-aryl-tetrafluoropyridines (8, aryl = Ph; 9, aryl = Tol) and into 2,3,5,6-tetrafluoropyridine in the presence of the boronic acids PhB(OH)(2), TolB(OH)(2), or HBpin when 5 mol % of 2 is employed as catalyst.
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页码：1417 / 1424
页数：8
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