NHC Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling Reactions of Aryl Boronate Esters with Perfluorobenzenes

Zhou, Jing; Berthel, Johannes H. J.; Kuntze‐Fechner, Maximilian W.; Friedrich, Alexandra; Marder, Todd B.; Radius, Udo

doi:10.1021/acs.joc.6b01041

Cited by 86 publications

(36 citation statements)

References 72 publications

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“…Over the last decade, we have investigated stoichiometric as well as catalytic reactions of NHC (N‐heterocyclic carbene)‐stabilized nickel(0) complexes with partially and perfluorinated reagents . [Ni 2 ( i Pr 2 Im) 4 (μ‐COD)] ( i Pr 2 Im=1,3‐diisopropylimidazolin‐2‐ylidene), for example, undergoes oxidative addition of fluorinated arenes to form complexes of the type trans ‐[Ni( i Pr 2 Im) 2 F(C 6 F n H 6− n )] and readily catalyzes subsequent transformations, such as hydrodefluorination and Suzuki–Miyaura cross‐coupling . Furthermore, we recently reported the [Ni(Mes 2 Im) 2 ]‐catalyzed borylation of fluoroarenes through C−F bond cleavage and were able to isolate trans ‐ [Ni(Mes 2 Im) 2 F(C 6 F 3 H 2 )] as an intermediate in the catalytic cycle of this reaction (Scheme , A) .…”

Section: Introductionmentioning

confidence: 99%

Ligand versus Complex: C−F and C−H Bond Activation of Polyfluoroaromatics at a Cyclic (Alkyl)(Amino)Carbene

Paul

Radius

2017

Chemistry A European J

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C-F and C-H bond activation reactions of polyfluoroaromatics at the cyclic (alkyl)(amino)carbene (cAAC) cAAC (1) are reported. Studies on the C-F bond activation using the cAAC-stabilized nickel(0) complex [Ni(cAAC ) ] (2) have shown that 2 does not react with fluorinated arenes. However, these investigations led to the observation of C-F bond cleavage of perfluorinated arenes by the carbene ligand cAAC (1) itself. The reaction of 1 with C F , C F -C F , C F -CF , and C F N afforded the insertion products of cAAC into one of the C-F bonds of the substrate, that is, the C-F bond activation products (cAAC )F(Ar ) (Ar =C F 4 a, C F -C F 4 b, C F -CF 4 c, C F N 4 d). These products decompose readily upon heating to 80 °C within a few hours in solution with formation of ionic iminium salts [(cAAC )(Ar )][X] 6 a-d or neutral alkenyl perfluoroaryl imine compounds 7 a-d. The compounds (cAAC )F(Ar ) 4 a-d readily transfer fluoride, which has been exemplified by the fluoride transfer of all compounds using BF etherate as fluoride acceptor. Fluoride transfer has also been achieved starting from (cAAC )F(C F -CF ) (4 c) or (cAAC )F(C F N) (4 d) to other selected substrates such as trimethylchlorosilane, benzoyl chloride and tosyl chloride. Instead of C-F bond activation, insertion of the cAAC into the C-H bond was observed if 1 was treated with the partially fluorinated arenes C F H, 1,2,4,5-C F H , 1,3,5-C F H , and 1,3-C F H . The compounds (cAAC )H(Ar ) (Ar =C F 12 e, 2,3,5,6-C F H 12 f, 2,4,6-C F H 12 g and 2,6-C F H 12 h) have been isolated in good yields and have been characterized including X-ray analysis. Fluorobenzene C FH (pK ≈37), the least C-H acidic fluoroarene used in this study, does not react. In order to investigate the scope and limitations of this type of cAAC C-H bond activation reaction, cAAC (1) was treated with several other reagents of different C-H acidity such as imidazolium salts, imidazoles, esters, and trimethylphosphine. These investigations led to the isolation and characterization of the compounds [(cAAC )H(R Im )]X (13 a,b), (cAAC )H(Im ) (14 a-c), (cAAC )H(CH(COOCH ) ) (15 b) and (cAAC )H(CH -PMe ) (16). Deprotonation of [(cAAC )H(Me Im )][BF ] (13 a) at the cAAC carbon atom using KHMDS as a base led to isolation and structural characterization of the cAAC -NHC heterodimer (17).

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Section: Introductionmentioning

confidence: 99%

Ligand versus Complex: C−F and C−H Bond Activation of Polyfluoroaromatics at a Cyclic (Alkyl)(Amino)Carbene

Paul

Radius

2017

Chemistry A European J

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“…Transition metal-catalysed Ar-F functionalization is considerably more challenging than classical Ar-H or Ar-Hal (Hal = I, Br, Cl) activation, generally showing low selectivities and requiring electronically biased polyfluorinated substrates. [5][6][7] In particular, C-C formation reaction via C-F cleavage of fluoroarenes using nickel catalyst has been reported for Kumada-Corriu, [8][9][10][11][12][13][14][15][16] Suzuki-Miyaura [17][18][19][20][21][22] and Negishi 23 cross-coupling reactions. However, all these methods use activated aryl nucleophiles, such as highly reactive Grignard reagents, zincates and boronic acids as the coupling partner for C-C formation via transmetallation (Scheme 1a).…”

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Chemodivergent Nickel(0)-Catalyzed Arene C–F Activation with Alkynes: Unprecedented C–F/C–H Double Insertion

et al. 2019

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Nickel-catalyzed C-F activations enabled chemo-divergent CC formation with alkynes by chelation assistance. The judicious choice of the alkynes electronic properties allowed the selective synthesis of double-insertion aromatic homologation or alkyne mono-annulation products by C-F/C-H activation. Based on the unambiguous crystallographic characterization of an unprecedented 9-membered nickelocyclic intermediate and extensive DFT studies, a plausible mechanistic rationale was established for the selective C-F activation and the chemodivergent catalysis.

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“…61 The deactivation mechanisms of catalysts based on 4d and 5d metals can thus provide useful insight for the development of new systems based on the cheaper and less toxic 3d metals. 62,63,64,65,66,67 Despite the biased attention of mechanistic studies towards on-cycle steps, a fair amount of data is already available for off-cycle deactivation reactions. The topic was recently reviewed by Crabtree, who classified these reactions on the basis of their cause, including ligand-centered reactions and inhibition by different agents, and discussed how they can be excluded or mitigated.…”

Section: Sophisticated Models Based On Quantum Mechanics Calculationsmentioning

confidence: 99%

Designing Pd and Ni Catalysts for Cross-Coupling Reactions by Minimizing Off-Cycle Species

Balcells

Nova

2018

ACS Catal.

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This perspective presents an overview on recent experimental and computational studies on the off-cycle reactions of palladium-and nickel-catalyzed cross-couplings. Several reactions entering or leaving the catalytic cycle have been characterized, including the activation of Pd(II) precatalysts by H-shift and the deactivation of Ni(II) precatalysts by comproportionation. A fundamental difference between the off-cycle chemistries of palladium and nickel is the larger diversity of species yielded by the latter, with a rich combination of different oxidation states, nuclearity and ligand coordination modes. The molecular-level understanding of off-cycle reactions has enabled new catalyst design strategies, including the stereoelectronic fine-tuning of the ligands aimed at maximizing the activation of the precatalyst meanwhile preventing its deactivation. Despite several challenges, which concern both experiments (e.g. isolation and characterization of transient species) and computations (e.g. comprehensive mapping of the potential energy surface), this approach has already been applied with success in the optimization of popular catalytic platforms (e.g. NHC-Pd-allyl precatalysts) and shows promise for the development of highly active and robust catalysts based on nickel.

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NHC Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling Reactions of Aryl Boronate Esters with Perfluorobenzenes

Cited by 86 publications

References 72 publications

Ligand versus Complex: C−F and C−H Bond Activation of Polyfluoroaromatics at a Cyclic (Alkyl)(Amino)Carbene

Ligand versus Complex: C−F and C−H Bond Activation of Polyfluoroaromatics at a Cyclic (Alkyl)(Amino)Carbene

Chemodivergent Nickel(0)-Catalyzed Arene C–F Activation with Alkynes: Unprecedented C–F/C–H Double Insertion

Designing Pd and Ni Catalysts for Cross-Coupling Reactions by Minimizing Off-Cycle Species

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