Preparing (Multi)Fluoroarenes as Building Blocks for Synthesis: Nickel-Catalyzed Borylation of Polyfluoroarenes via C–F Bond Cleavage

Zhou, Jing; Kuntze‐Fechner, Maximilian W.; Bertermann, Rüdiger; Paul, Ursula S. D.; Berthel, Johannes H. J.; Friedrich, Alexandra; Du, Zhen-Ting; Marder, Todd B.; Radius, Udo

doi:10.1021/jacs.6b02337

Cited by 184 publications

(110 citation statements)

References 43 publications

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“…[2] One of the most straightforward approaches for facile diversification is to transform carboxylic acids into multitransformable intermediates such as organoboron compounds,w hich serve as versatile synthetic intermediates demonstrating aw ide spectrum of reactivities (Scheme 1A). [3] Indeed, recent studies, [4][5][6][7][8][9][10] including ours, [9b, 10a] on catalytic borylative transformations by cleavage of stable bonds,s uch as CÀH, [5] CÀO, [6] CÀN, [7] CÀCN, [8] CÀF, [9] and CÀS [10] bonds,h ave confirmed the validity of this approach. Herein, we report ad ecarbonylative borylation of aromatic thioesters that enabled two-step decarboxylative borylation of aromatic carboxylic acids.…”

supporting

confidence: 69%

Rhodium‐Catalyzed Decarbonylative Borylation of Aromatic Thioesters for Facile Diversification of Aromatic Carboxylic Acids

Ochiai¹,

Uetake²,

Niwa³

et al. 2017

Angewandte Chemie

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Transformation of aromatic thioesters into arylboronic esters was achieved efficiently using ar hodium catalyst. The broad functional-group tolerance and mild conditions of the method have allowed for the two-step decarboxylative borylation of aw ide range of aromatic carboxylic acids,including commercially available drugs.The carboxylic acid is afundamental functional group often found in abroad range of organic molecules,including natural products,p harmaceuticals,a grochemicals,a nd functional materials.The availability of carboxylic acids has been further increased by recent advances in carboxylation reactions.[1] In line with the increasing availability of carboxylic acids,t heir direct decarboxylative functionalization, which significantly expands the diversity of synthesizable molecules,h as also been attracting considerable interest.[2] One of the most straightforward approaches for facile diversification is to transform carboxylic acids into multitransformable intermediates such as organoboron compounds,w hich serve as versatile synthetic intermediates demonstrating aw ide spectrum of reactivities (Scheme 1A).[3] Indeed, recent studies, [4][5][6][7][8][9][10] including ours, [9b, 10a] on catalytic borylative transformations by cleavage of stable bonds,s uch as CÀH, [5] CÀO, [6] CÀN, [7] CÀCN, [8] CÀF, [9] and CÀS [10] bonds,h ave confirmed the validity of this approach. Herein, we report ad ecarbonylative borylation of aromatic thioesters that enabled two-step decarboxylative borylation of aromatic carboxylic acids.Thechallenge of this transformation was to cleave astable C(aromatic)ÀC(carbonyl) bond while forming an easily transformable CÀBb ond. Although various transition-metalcatalyzed decarboxylative transformations of aromatic carboxylic acids have been reported, [2] these transformations were achieved at elevated temperature (typically > 150 8 8C), which greatly limits the scope of applicable substrates.[11] This is probably because al arge amount of energy is required to cleave the stable CÀCb ond. To achieve the CÀCb ond cleavage under milder conditions,w ef ocused on transitionmetal-mediated decarbonylation by acylmetal species I (Scheme 1B).[12] We anticipated that reverse insertion of acarbonyl group in I could smoothly occur by the cleavage of the CÀCb ond under mild conditions to afford arylmetal species II, [2a, 13] which could react with adiboron compound to furnish the borylated product 3.[10a] Recently,S hi et al. and Rueping et al. independently reported nickel-catalyzed decarbonylative borylations based on this approach using esters and amides as precursors for the acylmetal species. However,t hese reactions still required high temperature (> 150 8 8C) with moderate substrate scope. [14] We envisioned that thioester 2,which is astable carboxylic acid derivative, [15] would be abetter precursor of the acylmetal species I because highly chemoselective cleavage of aC (carbonyl) À Sb ond in thioester 2 by oxidative addition to al ow-valent transition metal was anticipated to ...

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supporting

confidence: 69%

Rhodium‐Catalyzed Decarbonylative Borylation of Aromatic Thioesters for Facile Diversification of Aromatic Carboxylic Acids

Ochiai¹,

Uetake²,

Niwa³

et al. 2017

Angewandte Chemie

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“…5) Hydroborylation may occur to produce dearomatization products if a proton was located at the para ‐position of an electron‐withdrawing group ( 1 t, 1 x, 1 y, and 1 aa ). Notably, in some cases, such as 3 c and 3 j , the regioselectivity is different from that obtained with the transition‐metal‐catalyzed processes where ortho defluoroborylation was observed, providing an orthogonal strategy for regioselective defluoroborylation of polyfluoroarenes.…”

Section: Resultsmentioning

confidence: 85%

Visible‐Light‐Induced Selective Defluoroborylation of Polyfluoroarenes, gem‐Difluoroalkenes, and Trifluoromethylalkenes

et al. 2020

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Fluorinated organoboranes serve as versatile synthetic precursors for the preparation of value‐added fluorinated organic compounds. Recent progress has been mainly focused on the transition‐metal catalyzed defluoroborylation. Herein, we report a photocatalytic defluoroborylation platform through direct B−H activation of N‐heterocyclic carbene boranes, through the synergistic merger of a photoredox catalyst and a hydrogen atom transfer catalyst. This atom‐economic and operationally simple protocol has enabled defluoroborylation of an extremely broad scope of multifluorinated substrates including polyfluoroarenes, gem‐difluoroalkenes, and trifluoromethylalkenes in a highly selective fashion. Intriguingly, the defluoroborylation protocol can be transition‐metal free, and the regioselectivity obtained is complementary to the reported transition‐metal‐catalysis in many cases.

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“…Notable exceptions are NHC-ligated Ni(0) dimers from the group of Radius; such COD-bridged species are able to facilitate the Suzuki–Miyaura coupling of benzyl chloride electrophiles 168 or perfluorinated arene electrophiles 169 . Radius 170 has also reported the monomeric precatalyst [Ni(IMes) 2 ] for the borylation of aryl fluorides. In terms of heteroleptic precatalysts, both the Buchwald–Hartwig amination of aryl tosylates 171 and the C–N coupling of indoles and carbazoles with aryl chlorides 172 can be mediated by the precatalyst [(IPr)Ni(η 2 -styrene) 2 ].…”

Section: Ni-based Precatalystsmentioning

confidence: 99%

Well-defined nickel and palladium precatalysts for cross-coupling

2017

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Transition metal-catalysed cross-coupling is one of the most powerful synthetic methods and has led to vast improvements in the synthesis of pharmaceuticals, agrochemicals and precursors for materials chemistry. A major advance in cross-coupling over the past 20 years is the utilization of well-defined, bench-stable Pd and Ni precatalysts that do not require the addition of free ancillary ligand, which can hinder catalysis by occupying open coordination sites on the metal. The development of precatalysts has resulted in new reactions and expanded substrate scopes, enabling transformations under milder conditions and with lower catalyst loadings. This Review highlights recent advances in the development of Pd and Ni precatalysts for cross-coupling, and provides a critical comparison between the state of the art in Pd- and Ni-based systems.

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Preparing (Multi)Fluoroarenes as Building Blocks for Synthesis: Nickel-Catalyzed Borylation of Polyfluoroarenes via C–F Bond Cleavage

Cited by 184 publications

References 43 publications

Rhodium‐Catalyzed Decarbonylative Borylation of Aromatic Thioesters for Facile Diversification of Aromatic Carboxylic Acids

Rhodium‐Catalyzed Decarbonylative Borylation of Aromatic Thioesters for Facile Diversification of Aromatic Carboxylic Acids

Visible‐Light‐Induced Selective Defluoroborylation of Polyfluoroarenes, gem‐Difluoroalkenes, and Trifluoromethylalkenes

Well-defined nickel and palladium precatalysts for cross-coupling

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