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Photoredox Catalysis Unlocks the Nickel-Catalyzed Cyanation of Aryl Halides under Benign Conditions

2021; Chinese Chemical Society; Volume: 4; Issue: 5 Linguagem: Inglês

10.31635/ccschem.021.202100934

2096-5745

Yue Jia, Yi‐Yin Liu, Liang‐Qiu Lu, Shihan Liu, Hongbin Zhou, Yu Lan, Wen‐Jing Xiao,

Sulfur-Based Synthesis Techniques

Open AccessCCS ChemistryCOMMUNICATION1 May 2022Photoredox Catalysis Unlocks the Nickel-Catalyzed Cyanation of Aryl Halides under Benign Conditions Yue Jia†, Yi-Yin Liu†, Liang-Qiu Lu†, Shi-Han Liu, Hong-Bin Zhou, Yu Lan and Wen-Jing Xiao Yue Jia† CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079 , Yi-Yin Liu† CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079 , Liang-Qiu Lu† CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079 , Shi-Han Liu School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 , Hong-Bin Zhou CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079 , Yu Lan *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 Province College of Chemistry, Institute of Green Catalysis, Zhengzhou University, Zhengzhou 450001 and Wen-Jing Xiao *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079 State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032 https://doi.org/10.31635/ccschem.021.202100934 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail The transition-metal-catalyzed cyanations of aryl halides are among the most used methods for synthesizing aryl nitriles. Despite tremendous advances, cyanating an aryl halide in a facile and benign fashion has generally been unsuccessful. The challenge in this significant transformation is the strong affinity of cyanide for metals, which hampers oxidative addition (OD) and reductive elimination (RE) making organometallic catalysis elusive. Herein, we demonstrate for the first time that photoredox–nickel-catalyzed cyanations of aryl halides are readily enabled by visible light, in which Ni(II) species are transiently oxidized to Ni(III) species, thereby facilitating subsequent cyanide transfer and RE. Using this dual catalysis strategy, we cyanated aryl and alkenyl halides at room temperature in a highly benign manner (30 examples, 53–93% yield) by avoiding the use of air-sensitive ligands, Ni(0) precursors, and hypertoxic cyanation reagents, while also limiting excess metal waste. Computational studies were also used to help understand the present transformation. Download figure Download PowerPoint Introduction The synthesis of aryl nitriles is among the most important tasks in synthetic chemistry, the pharmaceutical chemistry, and materials science.1–6 Regarding their pharmaceutical significance, aryl nitriles can be used to mimic androst-4-ene-3,17-diones and inhibit the aromatase enzyme by functioning as H-bond acceptors (Figure 1a).2,3 Accordingly, these motifs are commonly found in pharmaceutical agents, such as the anticancer drug enzalutamide and the anti-HIV drug rilpivirine, which were among the top 200 brand-name drugs by retail sales in 2019.7 In addition to their biochemical properties, aryl nitriles have also been widely used to construct metal–organic hybrid materials through efficient nitrile–metal coordination.4–6 For these reasons, many methods have been developed to access aryl nitriles.8 In particular, over the past few decades, transition-metal-catalyzed aryl halide cyanation has rapidly evolved into a convenient technology (Figure 1b).9–15 Despite tremendous advances in this field,16 from the perspective of green chemical synthesis, this technology still needs to be perfected. For example, when metal- or metalloid-bound cyanides (e.g., NaCN, KCN, trimethylsilyl cyanide (TMSCN), and K4[Fe(CN)3]) are used, synthetic chemists must consider problems regarding safety, reproducibility, and the production of excess metal waste.11,13,17–19 To solve these problems, organic cyanation reagents, such as acetone cyanohydrin, butyronitrile, hetero-atom-bound cyanides, and malononitrile derivatives, have been developed.12,14,20–26 Regrettably, special operating procedures (i.e., slow addition of acetone cyanohydrin), harsh reaction conditions, or air-sensitive ligands and catalyst precursors are usually required, which diminishes the practicality of these methodologies. Therefore, new and efficient catalysis systems are highly desirable and needed to generate aryl nitriles in a facile and benign fashion. Figure 1 | (a) Examples of nitrile-containing drugs. (b) Previous single transition-metal-catalyzed approaches. (c) Depicting nickel-catalyzed cyanation challenges. (d) The dual photoredox–nickel catalysis method developed in this work. Download figure Download PowerPoint After analyzing how cyanide coordinates to the transition metal, we concluded that the strong affinity of cyanide relative to other coupling components brings additional challenges (Figure 1c).9,10,27,28 With nickel catalysis as an example, the easy formation of Ni(0)- and Ni(II)-cyano complexes were found to hamper the elementary oxidative addition (OD) and reductive elimination (RE) processes in the catalytic cycle, as well as the formation of the Ni(0) catalyst from the Ni(II) precursor.27,28,a Over the past decade, dual photoredox–organometallic catalysis has been established as an important platform for cross-coupling reactions.29–44 Recently, we questioned whether this strategy could be used to cyanate aryl halides in a benign manner (Figure 1d) by exploiting the fundamentally new reactivity of transient organometallic intermediates in a previously unknown mechanistic pathway.45–48 We propose the mechanism depicted in Figure 2 for a novel photoredox–nickel-catalyzed cyanation reaction. OD of Ni(0) catalyst A to aryl halide 1 generates Ar-Ni(II) intermediate B.49 At the same time, the ground-state photocatalyst ( PC) is excited by visible light to form the excited-stated photocatalyst ( PC*). At this juncture, we expect that the single electron transfer (SET) between Ar-Ni(II) species B and the oxidizing PC* proceeds smoothly to provide the critical Ni(III)-Ar species C and the reduced photocatalyst PC−,50–55 after which the generated Ar-Ni(III) species accepts a cyano (CN) group from the cyanation reagent 2. Once formed, the transient Ar-Ni(III)-CN complex D rapidly undergoes RE to provide the desired product 3. Finally, both the nickel and photoredox catalysis cycles close after a second SET process involving Ni(I) species E and the reduced photocatalyst PC−. We speculate that controlled metal–CN coordination and accelerated RE are two key processes that will facilitate this strategy. Figure 2 | Proposed mechanism for the photoredox–nickel-catalyzed cyanation. Download figure Download PowerPoint Results and Discussion Condition optimization With the above-mentioned concept in mind, we began to investigate the dual catalytic cyanation method using ethyl 4-bromobenzoate ( 1a) as the substrate and the α-aminoacetonitrile 2a as the cyanide source. Indeed, the combination of an Ir-photocatalyst, a nickel catalyst, and irradiation [6 W blue light-emitting diodes (LEDs) at room temperature (rt)] provided ethyl 4-cyanobenzoate ( 3a) in 16% yield (Table 1, entry 1). To improve the reaction efficiency, we screened analogues 2b and 2c; thus, α-aminoacetonitrile 2b, which had been inefficient in previous Ni-catalyzed cyanations,56,57 was clearly the best cyanide source, with 3a obtained in 48% yield (Table 1, entry 2). Investigating the effects of various solvents revealed that tetrahydrofuran (THF) was optimal (Table 1, entry 8: 56% yield). Numerous basic additives were subsequently examined and an organic base, iPr2NEt, was found to be the optimal additive (Table 1, entry 12: 89% yield). The use of mild conditions and a weak base indicates that a cyano-transfer mechanism different from the usual one operates here (vide infra).56–58 Furthermore, other commonly used cyanation reagents, namely TMSCN, K4[Fe(CN)6]), and tetrabutylammonium cyanide (TBACN), were examined under the optimal conditions (Table 1, entries 13 and 14); however, no aryl nitrile product was obtained, presumably due to difficultly in cyanide-anion dissociation (K4[Fe(CN)6]) or the deactivation of the nickel catalyst by the presence of excess cyanide anion (TBACN and TMSCN). Control experiments using α-aminoacetonitrile 2b confirmed that this benign cyanation reaction is a typical visible-light-driven dual catalysis process. Table 1 | Condition Optimization for the Photoredox–Nickel-Catalyzed Cyanationa Entry CN Source Solvent Additiveb Yield (%)c 1 2a MeCN — 16 2 2b MeCN — 48 3 2c MeCN — 32 4 2d MeCN — Trace 5 2b CH2Cl2 — 8 6 2b DMF — 40 7 2b DMSO — 36 8 2b THF — 56 9 2b THF K2CO3 61 10 2b THF K3PO4 60 11 2b THF Et3N 67 12 2b THF iPr2NEt 89 13 4a–4c THF iPr2NEt 0 14d 4a THF iPr2NEt 0 15e 2b THF iPr2NEt 0 Note: dF(CF3)ppy, 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; dtbbpy, 4,4′-ditert-butyl-2,2′-bipyridine; 4a, TMSCN; 4b, K4[Fe(CN)6]; 4c, TBACN; MeCN, acetonitrile; CH2Cl2, dichloromethane; DMF, dimethylformamide; DMSO, dimethylsulfoxide. aReaction conditions: 1a (0.5 mmol), 2 (0.75 mmol, 1.5 equiv), NiCl2•glyme (0.025 mmol, 5 mol %), dtbbpy (0.025 mmol, 5 mol %), Ir[dF(CF3)ppy2(dtbbpy)]PF6 (0.01 mmol, 2 mol %), and solvent (4 mL) under irradiation by 6 W blue LEDs. bUse of 2.0 equiv of additive. cIsolated yield of 3a. dAddition of 1.5 equiv of CsF. eControl experiments in the absence of nickel catalyst, photocatalyst, or light. Generality of methodology We next turned our attention to examining the generality of this new photoredox–nickel-catalyzed cyanation process under the optimal reaction conditions. As shown in Figure 3, electron-deficient aryl bromides bearing a variety of functional groups (e.g., ester, ketone, and fluorine) and electro-neutral bromobenzene participate in this reaction well (Figure 3a, 3a– 3d: 82–90% yield). Moreover, a diverse array of electron-rich bromoarenes with various substituents at the para-position of the benzene ring (e.g., methyl, methoxy, benzyloxy, tosylamido, and phenyl) were found to be effective substrates in this cyanation reaction (Figure 3a, 3e– 3i: 76–93%). Varying the substitution position and manner (e.g., 3,4-dioxole, 2-chloro or phenyl, 3-vinyl, 2-naphthyl) resulted in no obvious loss in efficiency (Figure 3a, 3j– 3n: 76–93%). Perhaps more importantly, this photoredox–nickel-catalyzed reaction can be further used to cyanate heteroaryl bromides. For example, bromoarenes containing a wide range of heteroaromatic rings (indole, carbazole, benzothiophene, benzothiazole, quinoline, and pyridine) were compatible with this reaction system (Figure 3b, 3o– 3u: 65–91%). In addition to the above-mentioned monobromo aromatic substrates, 1,4-dibromobenzene, and 2,6-dibromopyridine were competent substrates and provided the corresponding dicyano products with high reaction efficiencies (Figure 3c, 3v: 75%; 3w: 67%). Note that this double cyanation process was successfully applied to the synthesis of an anticancer drug, letrozole, from commercially available bis(4-bromophenyl)methanone (see Supporting Information for details). To our delight, the same catalyst system successfully cyanated alkenyl bromides (Figure 3c, 3x: 80%; 3y: 90%). At the current stage, activated aryl chlorides were also amenable to this cyanation reaction in the presence of the additive NaBr (Figure 3d, 3a– 3e: 53–90% yields).b Figure 3 | (a–d) Demonstration of the generality of photoredox–nickel-catalyzed cyanation. aUsing 2.2 equiv of cyanide source 2b. b55 °C, 24 h. cAdding 2.0 equiv of NaBr. d55 °C, 72 h. Download figure Download PowerPoint Mechanism studies To gain further insight into the mechanism of the cyanation reactions, we turned our attention to studying the role of Ir-photocatalyst (Ir[dF(CF3)ppy2(dtbbpy)]PF6) [dF(CF3)ppy, 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; dtbbpy, 4,4′-ditert-butyl-2,2′-bipyridine]. According to our mechanistic hypothesis, excited-state photocatalyst *Ir[dF(CF3)ppy2(dtbbpy)]PF6 acts as an oxidant to oxidize Ni(II)-Ar species B into transient Ni(III)-Ar species C (Figure 4). To test this, we synthesized Ni(II) complex 5a from corresponding Ni(0) precursor Ni(cod)2, aryl bromide, and dtbbpy ligand (see Supporting Information Figures S1–S3 and other details in Supporting Information).59,c Stern–Volmer quenching studies showed that Ni(II) complex 5a can effectively quench *Ir[dF(CF3)ppy2(dtbbpy)]PF6, and therefore, we propose that Ni(II)-Ar species B might undergo single-electron oxidation by the excited photocatalyst, forming the Ni(III)-Ar species C. Next, we performed a series of control experiments with Ni(II) complex 5a. First, treatment of 1 equiv of Ni(II) complex 5a and 5 mol % of Ir[dF(CF3)ppy2(dtbbpy)]PF6 with 2 equiv of iPr2NEt in THF under visible light irradiation led to formation of the product 3a in 79% yield [Figure 5, (1)]. Second, the absence of visible light irradiation or Ir photocatalyst under the same reaction conditions only led to a trace amount of product 3a [Figure 5, (2) and (3)]. Third, the replacement of NiCl2 and dtbbpy with Ni(II) complex 5a under standard reaction conditions led to 42% yield of the product 3a [Figure 5, (4)]. According to these experimental evidences, we believe that Ni(II) complex 5a might work as a possible intermediate in the catalytic cycle, and photoredox catalysis helps promote the nickel-catalyzed cyanation. Figure 4 | Luminescence quenching experiments. Download figure Download PowerPoint Figure 5 | Stoichiometric and catalytic experiments with Ni(II) complex. Download figure Download PowerPoint After that, we turned to computational chemistry using density functional theory (DFT) (see Supporting Information Figure S4 and other details in Supporting Information) to better understand this unprecedented cyanation reaction, the results of which are summarized in Figure 6. Free energies are referenced against [Ni(0)-1b],60,61,d,e the most thermodynamically stable substrate-coordinated complex. The direct OD was calculated to have a free-energy barrier of 11.2 kcal/mol and occurs via 4-ts, a three-membered-ring transition state, to generate aryl-Ni(II) complex 5. In path A, this complex is oxidized by the triplet *[Ir(III)] + photocatalyst through SET to afford aryl-Ni(III) complex 6 through an 8.4 kcal/mol exothermic process. This result suggests that the SET process is feasible both thermodynamically and kinetically. Reactant 2b coordinates to 6 to form intermediate 7 in a process that is exothermic by 2.4 kcal/mol. Subsequent C–C-bond cleavage via transition state 8-ts, with an overall barrier of 13.9 kcal/mol, forms the isocyano-Ni(III) intermediate 10 with the release of the iminium cation 9. Subsequent isomerization proceeds via the three-membered-ring transition state 11-ts to form the cyano-Ni(III) intermediate 12. These results explain why the cyano group in this reaction is transferred at rt without the assistance of a strong base, such as K3PO4. RE subsequently takes place with a free-energy barrier of only 2.7 kcal/mol through 13-ts, and this spontaneous process is exergonic by approximately 30 kcal/mol to form product 3b and the Ni(I) complex. Finally, the Ni(I) complex is reduced by [Ir(II)] through SET to complete the nickel catalysis and photoredox catalysis cycles. For comparison, we also investigated another possible catalysis cycle involving Ni(II) complexes (path B). After generating the aryl-Ni(II) complex 5, subsequent C–C bond cleavage occurs via transition state 15-ts, with an activation free energy of 33.8 kcal/mol; however, the activation free energy of this pathway is 21.8 kcal/mol higher than that involving 11-ts, which indicates that cyano-group transfer from α-aminoacetonitrile 2b to the Ni(II) species ( 14 → 19) is much more difficult than transfer to the Ni(III) variant ( 7 → 12). Subsequent RE of Ni(II) species 19 has a free-energy barrier of 29.4 kcal/mol (through 20-ts), which is much higher than that involving Ni(III) species 12 through 13-ts (2.7 kcal/mol). Therefore, this catalysis cycle (path B) is kinetically and thermodynamically disfavored compared to the aforementioned process (path A). Figure 6 | DFT calculations for the photoredox–nickel-catalyzed cyanation of aryl halides. Download figure Download PowerPoint Conclusion We successfully developed the first condition-benign cyanation reaction of aryl and alkenyl halides through dual photoredox–nickel catalysis. A wide range of structurally variant aryl and alkenyl nitriles were prepared using an operationally safe, metal-waste-free cyanide source. Moreover, spectroscopy studies, control experiments, and DFT calculations revealed details of the previously unknown reaction pathway and novel organometallic reactivity. Mechanistically, the key to the success of this chemistry is the use of the photoredox catalysis strategy for accessing transient Ni(III) aryl species, which facilitates previously elusive cyanide transfer from an α-aminoacetonitrile and subsequent RE in nickel catalysis chemistry. Footnotes a Our computational studies revealed that the reductive elimination of LNi(II)Ar(CN) species is an endothermic process that is thermally unfavorable compared with the Ni(III) variant (an exothermic process). b NaBr was proposed to facilitate the oxidative addition under nickel catalysis (see ref 19). Unfortunately, no conversion of aryl triflates and nonactivated aryl chlorides was detected under the present catalysis system. c For the preparation of Ni(II) complex 5a, see ref 59. We also have tried but failed to prepare the Ni(II)-CN complex from 5a. d Ni(II) catalyst precursor can be reduced by a low-valence iridium catalyst with the help of sacrificial reduction reagent, see ref 60. e For the reduction of Ni(II) precursor, see ref 61. Supporting Information Supporting Information is available and includes experimental procedures, characterization data, 1H NMR spectra, 13C NMR spectra, and high-resolution mass spectrometry for products. Conflict of Interest There is no conflict of interest to report. Funding Information This research was made possible by a generous grant from the National Science Foundation of China (nos. 21822103, 21820102003, 21822303, 21772052, 21772053, and 91956201), the Program of Introducing Talents of Discipline to Universities of China (111 Program, B17019), and the Natural Science Foundation of Hubei Province (no. 2017AHB047). 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Google Scholar Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 4Issue 5Page: 1577-1586Supporting Information Copyright & Permissions© 2021 Chinese Chemical SocietyKeywordscyanation reactionvisible lightaryl nitrilephotoredox catalysisnickel catalysisAcknowledgmentsThe authors are grateful to the International Joint Research Center for Intelligent Biosensing Technology and Health for support. The authors appreciate Prof. Jia-Rong Chen and Prof. Ying Cheng for suggestive discussions. Downloaded 3,338 times PDF DownloadLoading ...