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Iodobenzene-catalyzed photochemical heteroarylation of alcohols by rupture of inert C–H and C–C bonds

  • Zhu Cao
    Affiliations
    Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu, 215123, China
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  • Xinxin Wang
    Affiliations
    Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu, 215123, China
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  • Xinxin Wu
    Affiliations
    Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu, 215123, China
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  • Chen Zhu
    Correspondence
    Corresponding author. Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu, 215123, China.
    Affiliations
    Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu, 215123, China

    Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China
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Open AccessPublished:October 19, 2022DOI:https://doi.org/10.1016/j.tchem.2022.100031

      Abstract

      A Minisci-type reaction catalyzed by iodobenzene is disclosed here for the first time. The heteroarylation of unprotected aliphatic alcohols proceeds via alkoxy radical-induced homolytic cleavage of C–H and C–C bonds under photochemical conditions. The use of m-CPBA as the oxidant allows the oxidation of iodobenzene to a hypervalent iodine species, driving the catalytic cycle. The method features mild reaction conditions, broad scope of heteroarenes and alcohols, and scaled up preparations. This approach provides a notable supplement to iodobenzene-catalyzed ionic reactions, and opens up a new avenue for its application in radical chemistry.

      Graphical abstract

      Keywords

      1. Introduction

      The uniquely reactive hypervalent iodine reagents have attracted intense research interest and have frequently been exploited in the laboratory over the past few decades [
      • Yoshimura A.
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      Advances in synthetic applications of hypervalent iodine compounds.
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      Hypervalent iodine reagent-mediated reactions involving rearrangement processes.
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      Combined approach of hypervalentiodine reagents and transition metals in organic reactions.
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      • Dahiya A.
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      Updates on hypervalent-iodine reagents: metal-free functionalisation of alkenes, alkynes and heterocycles.
      ,
      • Allouche E.M.D.
      • Grinhagena E.
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      Hypervalent iodine-mediated late-stage peptide and protein functionalization.
      ,
      • Kumar R.
      • Singh F.V.
      • Takenaga N.
      • Dohi T.
      Asymmetric direct/stepwise dearomatization reactions involving hypervalent iodine reagents.
      ,
      • Dasgupta A.
      • Thiehoff C.
      • Newman P.D.
      • Wirth T.
      • Melen R.L.
      Reactions promoted by hypervalent iodine reagents and boron Lewis acids.
      ,
      • Zhao R.
      • Shi L.
      Reactions between diazo compounds and hypervalentIodine(III) reagents.
      ,
      • Han Z.-Z.
      • Zhang C.-P.
      Fluorination and fluoroalkylation reactions mediated by hypervalent iodine reagents.
      ,
      • Wang X.
      • Studer A.
      Iodine(III) reagents in radical chemistry.
      ,
      • Wu X.
      • Zhang H.
      • Tang N.
      • Wu Z.
      • Wang D.
      • Ji M.
      • Xu Y.
      • Wang M.
      • Zhu C.
      Metal-free alcohol-directed regioselective heteroarylation of remote unactivated C(sp3)-H bonds.
      ,
      • Ren R.
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      Manganese-catalyzed oxidative azidation of cyclobutanols: regiospecific synthesis of alkyl azides by C-C bond cleavage.
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      Manganese-catalyzed ring-opening chlorination of cyclobutanols: regiospecific synthesis of γ-chloroketones.
      ,
      • Wu Z.
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      Chemo- and regioselective distal heteroaryl ipso-migration: a general protocol for heteroarylation of unactivated alkenes.
      ,
      • Wang M.
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      • Zhang B.
      • Zhu C.
      Azidoheteroarylation of unactivated olefins through distal heteroaryl migration.
      ,
      • Wang D.
      • Mao J.
      • Zhu C.
      Visible light-promoted ring-opening functionalization of unstrained cycloalkanols via inert C-C bond scission.
      ,
      • Tang N.
      • Wu X.
      • Zhu C.
      Practical, Metal-free remote heteroarylation of amides via unactivated C(sp3)-H bond functionalization.
      ,
      • Shao X.
      • Wu X.
      • Wu S.
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      Metal-free radical-mediated C(sp3)-H heteroarylation of alkanes.
      ,
      • Cao Z.
      • Zhang H.
      • Wu X.
      • Li Y.
      • Zhu C.
      Radical heteroarylation of unactivated remote C(sp3)-H bonds via intramolecular heteroaryl migration.
      ,
      • Chang C.
      • Zhang H.
      • Wu X.
      • Zhu C.
      Radical trifunctionalization of hexenenitrile via remote cyano migration.
      ,
      • Wang X.
      • Shao X.
      • Cao Z.
      • Wu X.
      • Zhu C.
      Metal-free photoinduced deformylative Minisci-type reaction.
      ,
      • Cao Z.
      • Ji M.
      • Wang X.
      • Wu X.
      • Li Y.
      • Zhu C.
      Metal-free photo-induced heteroarylations of C-H and C-C bonds of alcohols by flow chemistry.
      ]. However, some inherent disadvantages, such as their explosive properties, storage difficulties, high expense and poor solubility, have led to concerns about using the reagents. The large amount of aryl iodide discarded as byproduct in the reaction also raises environmental issues, which limit their applications in industry. Iodobenzene is a readily available and inexpensive synthetic feedstock. It has been sometimes employed as an organocatalyst instead of a source of stoichiometric amounts of hypervalent iodine reagents in ionic reactions, which include C–H bond amination [
      • Zhu C.
      • Liang Y.
      • Hong X.
      • Sun H.
      • Sun W.-Y.
      • Houk K.N.
      • Shi Z.
      Iodoarene-catalyzed stereospecific intramolecular sp3 C-H amination: reaction development and mechanistic insights.
      ], biaryl synthesis by C–C bond coupling [
      • Ito M.
      • Kubo H.
      • Itani I.
      • Morimoto K.
      • Dohi T.
      • Kita Y.
      Organocatalytic C-H/C-H’ cross-biaryl coupling: C-selective arylation of sulfonanilides with aromatic hydrocarbons.
      ], construction of spiro-heterocyclic compounds via dearomatization of phenols [
      • Dohi T.
      • Maruyama A.
      • Yoshimura M.
      • Morimoto K.
      • Tohma H.
      • Kita Y.
      Versatile hypervalent-iodine(iii)-catalyzed oxidations with m-chloroperbenzoic acid as a cooxidant.
      ], α-acetoxylation/tosyloxylation/fluorination of ketones [
      • Ochiai M.
      • Takeuchi Y.
      • Katayama T.
      • Sueda T.
      • Miyamoto K.
      Iodobenzene-catalyzed α-acetoxylation of ketones. In situ generation of hypervalent (diacyloxyiodo)benzenes using m-chloroperbenzoic acid.
      ,
      • Yamamoto Y.
      • Kawano Y.
      • Toy P.H.
      • Togo H.
      PhI- and polymer-supported PhI-catalyzed oxidative conversion of ketones and alcohols to α-tosyloxyketones with m-chloroperbenzoic acid and p-toluenesulfonic acid.
      ,
      • Suzuki S.
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      • Kita Y.
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      Iodoarene-catalyzed fluorination and aminofluorination by an Ar-I/HF.pyridine/mCPBA system.
      ], Hoffman rearrangement [
      • Miyamoto K.
      • Sakai Y.
      • Goda S.
      • Ochiai M.
      A catalytic version of hypervalent aryl-λ3-iodane-induced Hofmann rearrangement of primary carboxamides: iodobenzene as an organocatalyst and m-chloroperbenzoic acid as a terminal oxidant.
      ], dibromination and oxidative cleavage of alkenes or alkynes [
      • Stodulski M.
      • Goetzinger A.
      • Kohlhepp S.V.
      • Gulder T.
      Halocarbocyclization versus dihalogenation: substituent directed iodine(III) catalyzed halogenations.
      ,
      • Miyamoto K.
      • Sei Y.
      • Yamaguchi K.
      • Ochiai M.
      Iodomesitylene-catalyzed oxidative cleavage of carbon-carbon double and triple bonds using m-chloroperbenzoic acid as a terminal oxidant.
      ], and oxidation of alcohols [
      • Page P.C.B.
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      In situ generation of 2-iodoxybenzoic acid (IBX) in the presence of tetraphenylphosphonium monoperoxysulfate (TPPP) for the conversion of primary alcohols into the corresponding aldehydes.
      ,
      • Thottumkara A.P.
      • Bowsher M.S.
      • Vinod T.K.
      In situ generation of o-iodoxybenzoic acid (IBX) and the catalytic use of it in oxidation reactions in the presence of oxone as a Co-oxidant.
      ] (Scheme 1A). In these reactions, iodobenzene is oxidized by strong oxidants, such as m-CPBA, to hypervalent iodine, a III or V species, perpetuating the catalytic cycle. Despite these achievements, radical-mediated transformations catalyzed by iodobenzene have been reported only rarely [
      • Narobe R.
      • Murugesan K.
      • Schmid S.
      • König B.
      Decarboxylative Ritter-type amination by cooperative iodine (I/III)-boron Lewis acid catalysis.
      ,
      • Narobe R.
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      C(sp3)-H Ritter amination by excitation of in situ generated iodine (lll)-BF3 complexes.
      ,
      • Shen C.
      • Yang M.
      • Xu J.
      • Chen C.
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      • Shen J.
      • Zhang P.
      Iodobenzene-catalyzed synthesis of aryl sulfonate esters from aminoquinolines via remote radical C-O cross-coupling.
      ,
      • Jin J.
      • Tong J.
      • Yu W.
      • Qiao J.
      • Shen C.
      Iodobenzene-catalyzed oxidative C-H d3-alkoxylation of quinoxalinones with deuterated alcohols.
      ], presumably because of the functional group incompatibility in the presence of strong oxidants.
      Scheme 1
      Scheme 1Iodobenzene-catalyzed reactions.
      Heteroarenes are ubiquitous in natural products and molecules such as pharmaceuticals and organic materials. Construction of structurally diverse heteroarenes is important in organic chemistry [
      • Peerzada M.N.
      • Hamel E.
      • Bai R.
      • Supuran C.T.
      • Azam A.
      Deciphering the key heterocyclic scaffolds in targeting microtubules, kinases and carbonic anhydrases for cancer drug development.
      ,
      • Stępień M.
      • Gońka E.
      • Żyła M.
      • Sprutta N.
      Heterocyclic nanographenes and other polycyclic heteroaromatic compounds: synthetic routes, properties, and applications.
      ,
      • Waldman A.J.
      • Ng T.L.
      • Wang P.
      • Balskus E.P.
      Heteroatom-heteroatom bond formation in natural product biosynthesis.
      ,
      • McGrath N.A.
      • Brichacek M.
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      A graphical journey of innovative organic architectures that have improved our lives.
      ,
      • Ward R.A.
      • Kettle J.G.
      Systematic enumeration of heteroaromatic ring systems as reagents for use in medicinal chemistry.
      ]. Recently, the Minisci reaction has witnessed a rapid growth of synthetic efforts using the reaction, and supplies a robust tool for heteroarene modification by incorporating alkyl groups into nitrogenous heteroarenes [
      • Proctor R.S.J.
      • Phipps R.J.
      Recent advancesin Minisci-type reactions.
      ,
      • Dong J.
      • Liu Y.
      • Wang Q.
      Recent advances in visible-light-mediated Minisci reactions.
      ,
      • Meng W.
      • Xu K.
      • Guo B.
      • Zeng C.
      Recent advances in Minisci reactions under electrochemical conditions.
      ,
      • Wang W.
      • Wang S.
      Recent advances in Minisci-type reactions and applications in organic synthesis.
      ,
      • Li G.-X.
      • Morales-Rivera C.A.
      • Wang Y.
      • Gao F.
      • He G.
      • Liu P.
      • Chen G.
      Photoredox-mediated Minisci C-H alkylation of N-heteroarenes using boronic acids and hypervalent iodine.
      ,
      • Fu M.-C.
      • Shang R.
      • Zhao B.
      • Wang B.
      • Fu Y.
      Photocatalytic decarboxylative alkylations mediated by triphenylphosphine and sodium iodide.
      ,
      • Cheng W.-M.
      • Shang R.
      • Fu M.-C.
      • Fu Y.
      Photoredox-catalysed decarboxylative alkylation of N-heteroarenes with N-(Acyloxy)phthalimides.
      ,
      • Li G.-X.
      • Hu X.
      • He G.
      • Chen G.
      Photoredox-mediated Minisci-type alkylation of N-heteroarenes with alkanes with high methylene selectivity.
      ,
      • Hu X.
      • Li G.-X.
      • He G.
      • Chen G.
      Minisci C-H alkylation of N-heteroarenes with aliphatic alcohols via β-scission of alkoxy radical intermediates.
      ]. Herein, we disclose a conceptually new iodobenzene-catalyzed Minisci reaction operating under photochemical conditions. The interaction of unprotected aliphatic alcohols with hypervalent iodine reagent, generated in situ from the oxidation of iodobenzene with.
      m-CPBA, is efficient and gives rise to alkoxy radicals, which subsequently engage in 1,5-hydrogen atom transfer (HAT) and β-C-C scission reactions. The radical heteroarylation reaction shows the good compatibility of heteroarenes and alcohols, leading to a variety of functionalized heteroarenes (Scheme 1B).

      2. Results and discussion

      We began the heteroarylation reaction with commercially available 4-chloroquinoline (1a) and n-pentanol (2a) as model substrates under blue LEDs irradiation (Table 1). Evaluation of the amount of alcohols indicated that excess alcohols were beneficial to improving the conversion (entries 1–3). Other functionalized aryl iodides with either electron-donating or withdrawing substituents did not offer superior catalytic efficiency than parent iodobenzene (entries 4–6). Benzenes bearing multiple iodides also did not result in better yields (entries 7–9). Replacing m-CPBA with other common oxidants, such as Oxone and K2S2O8, compromised the reaction outcomes (entries 10 and 11). Varying light source or performing the reaction without light, product 3a was obtained in low yields (entries 12–14). After a comprehensive survey of reaction conditions (for details, see the SI), the iodobenzene-catalyzed reaction proceeding via 1,5-HAT was found to deliver the best yield of the desired Minisci product (3a) in dichloromethane (DCM) using m-CPBA as oxidant and HBF4 as an additive.
      Table 1Reaction parameters screening.
      Reaction conditions: 1a (0.2 ​mmol), 2a (3.0 ​mmol), PhI (20 ​mol %), HBF4 (0.6 ​mmol, 48 ​wt % in H2O), and m-CPBA (0.64 ​mmol, added in four portions of 0.16 ​mmol each in 12 ​h intervals) in DCM (2.0 ​mL), irradiated by 2 ​× ​50 ​W blue LEDs at rt in N2 for 48 ​h.
      .
      Table thumbnail fx1
      a Reaction conditions: 1a (0.2 ​mmol), 2a (3.0 ​mmol), PhI (20 ​mol %), HBF4 (0.6 ​mmol, 48 ​wt % in H2O), and m-CPBA (0.64 ​mmol, added in four portions of 0.16 ​mmol each in 12 ​h intervals) in DCM (2.0 ​mL), irradiated by 2 ​× ​50 ​W blue LEDs at rt in N2 for 48 ​h.
      b Isolated yield.
      c 2a (1.0 ​mmol).
      d 2a (2.0 ​mmol).
      e 2 ​× ​30 ​W blue LEDs.
      f 30 ​W green LEDs.
      g In dark.
      With the optimized reaction conditions in hand, the generality of the protocol was assessed (Scheme 2, top). The C2-alkylation of quinoline derivatives bearing a C4-substituent smoothly proceeded via a 1,5-HAT regardless of the electronic characteristics, affording the corresponding products (3a-3e) in useful yields. The C4 position of quinolines could also be alkylated under the standard conditions, but delivered decreased yields of the products (3f-3i). Other heterocyclic compounds such as phenanthridine, pyridine and pyrazine containing two nitrogen atoms were converted into the desired products (3j-3l) respectively. The modification of a pesticide, fenazaquin (3m), was also achieved by this method. It was found that electron-rich heteroarenes such as benzothiazole and benzoxazole were not suitable substrates.
      Scheme 2
      Scheme 2Generality of the reaction via 1,5-HAT. Reaction conditions: 1 (0.2 ​mmol), 2 (3.0 ​mmol), PhI (20 ​mol %), HBF4 (0.6 ​mmol, 48 ​wt % in H2O), and m-CPBA (0.64 ​mmol, added in four portions of 0.16 ​mmol each in 12 ​h intervals) in DCM (2.0 ​mL), irradiated by 2 ​× ​50 ​W blue LEDs at rt in N2 for 48 ​h. Yields of isolated products are given.
      The heteroarylation of a set of aliphatic alcohols with 4-chloroquinoline was then examined (Scheme 2, bottom). The reaction of linear primary alcohols occurred regioselectively via 1,5-HAT regardless of the chain length, resulting in δ-heteroarylation (3n-3r). In the case of 3r, 1,5-HAT occurred exclusively prior to 1,6-HAT even in the presence of more reactive benzylic C–H bonds. In addition to secondary C–H bonds, tertiary and primary C–H bonds adjacent to an O atom also reacted (3s and 3t); the lower yields can probably be attributed to overoxidation of radical intermediates arising from HAT in the presence of strong oxidants. Notably, the reaction of primary C–H bonds with relatively higher bond dissociation energy (BDE) also proceeded, producing 3u, albeit in a lower yield. While alkoxy radicals derived from secondary alcohols are prone to trigger β-C-C fragmentation, secondary alcohols are tolerated in this protocol (3v). The examples of 3w and 3x are noteworthy, as the reactions occurred at a cyclopentyl or cyclohexyl ring, and furnished thermodynamically favored trans-products with excellent stereoselectivity (d.r. ​> ​20:1). Furthermore, this method supplies an efficient approach to the direct modification of cyclooctanol (3y).
      Subsequently, the alkylation of heteroarenes through β-C-C scission of alcohols was investigated (Scheme 3, top). Similar to the previous process involving a HAT, isopropylation at C2 or C4 of quinolines using isobutanol as alkyl radical source delivered comparable yields (5a-5h). Other N-containing heteroarenes such as phenanthridine, quinoxaline and pyrimidine reacted to afford the corresponding Minisci-type adducts (5i-5k). Remarkably, the antifungal agent, voriconazole (5l) could also be alkylated, illustrating the utility of this method in structural elaboration of complex molecular scaffolds.
      Scheme 3
      Scheme 3Generality of the reaction via β-C-C scission. Reaction conditions: 1 (0.2 ​mmol), 4 (3 ​mmol), PhI (20 ​mol %), HBF4 (0.6 ​mmol, 48 ​wt % in H2O), and m-CPBA (0.64 ​mmol, added in four portions of 0.16 ​mmol each in 12 ​h intervals) in DCM (2.0 ​mL), irradiated by 2 ​× ​50 ​W blue LEDs at rt in N2 for 48 ​h. Yields of isolated products are given.
      The performance of a variety of aliphatic alcohols was then evaluated in the formation of alkoxy radicals and subsequent β-C-C scission (Scheme 3, bottom). In addition to isobutanol, other isopropyl radical precursors, such as tertiary alcohols (4b-4d), also produced the desired product (5a) in good yields. Secondary aliphatic alcohols, such as 2-methyl-1-butanol (4e), 2-ethyl-1-butanol (4f), and an alcohol (4g) with benzyl C–H bonds susceptible to radical HAT or oxidation conditions, all are suitable substrates for β-C-C fragmentation and furnished the expected products (5m-5o), respectively. A set of cyclic secondary radicals generated from the corresponding alkanols (4h-4k) proceeded via β-C-C scission with ring opening, and were subsequently trapped by 4-chloroquinoline to give products (5p-5r). Interestingly, the bulky adamantyl radical derived from 1-adamantanemethanol (4l) could readily add to 4-chloroquinoline, leading to product (5s).
      To demonstrate the practicality of the synthetic method, two types of transformations, proceeding through 1,5-HAT or the β-C-C cleavage pathway were carried out under the standard conditions, giving synthetically useful yields (Scheme 4).
      The radical trapping experiment using 1,1-diphenylethylene as radical scavenger was carried out (Scheme 5). The reaction was almost completely inhibited, leading to trace amounts of 3a and the vinylation adduct detected by HRMS. The result may suggest the involvement of alkoxy radical in the transformation.
      Scheme 5
      Scheme 5Radical trapping experiment.
      The UV-VIS experiments were conducted to probe the formation of photo-absorbing species in the reaction (Scheme 6A). The interaction of PhI, m-CPBA, HBF4, and 2a generated a new species which displayed weak light absorption above 420 ​nm region. It suggested the possible energy transfer from blue LED to the new species which triggered the homolysis of I–O bond to generate alkoxy radical [
      • Wu X.
      • Zhang H.
      • Tang N.
      • Wu Z.
      • Wang D.
      • Ji M.
      • Xu Y.
      • Wang M.
      • Zhu C.
      Metal-free alcohol-directed regioselective heteroarylation of remote unactivated C(sp3)-H bonds.
      ].
      Scheme 6
      Scheme 6(A) UV-VIS experiments. (B) Proposed mechanisms.
      Based on the experimental results and previous reports, proposed mechanistic pathways are shown in Scheme 6B. Initially, the mixture of iodobenzene, m-CPBA and HBF4 generates a hypervalent species (A) [
      • Miyamoto K.
      • Sei Y.
      • Yamaguchi K.
      • Ochiai M.
      Iodomesitylene-catalyzed oxidative cleavage of carbon-carbon double and triple bonds using m-chloroperbenzoic acid as a terminal oxidant.
      ] and m-chlorobenzoic acid (m-CBA). The formation of [Ph-I-OH]+ species could be evidenced by HRMS analysis (see the SI). Interaction between A and aliphatic alcohol gives rise to an intermediate (B) with reactive iodine-oxygen bonds, which then undergoes homolysis under blue light irradiation to deliver alkoxy radical (C) (from 2a) or D (from 4a) [
      • Wu X.
      • Zhang H.
      • Tang N.
      • Wu Z.
      • Wang D.
      • Ji M.
      • Xu Y.
      • Wang M.
      • Zhu C.
      Metal-free alcohol-directed regioselective heteroarylation of remote unactivated C(sp3)-H bonds.
      ]. Meanwhile, iodobenzene is regenerated, continuing the catalytic cycle. The conversion of C to E via 1,5-HAT or D to F via β-C-C scission and subsequent interception of the alkyl radical (E or F) by the protonated heteroarene (G) gives rise to radical cation H or I, respectively. Single-electron oxidation of H or I by excess m-CPBA furnishes the final product 3a or 5a.

      3. Conclusion

      We are reporting an unprecedented protocol of iodobenzene-catalyzed Minisci-type reactions. The radical heteroarylation of C–H and C–C bonds in aliphatic alcohols proceeds readily under visible-light irradiation, and the inexpensive m-CPBA oxidizes iodobenzene to hypervalent iodine species, perpetuating the catalytic cycle. Many Minisci-type adducts have been obtained in synthetically useful yields. The protocol has many merits, including the use of a non-metallic organocatalyst, broad substrate scope, excellent regioselectivity, ability to expand the scale, and direct functionalization of complex structures. It should be mentioned that iodobenzene-catalyzed radical transformation is at a very early stage, and this approach opens up a new avenue for this research area.

      Data availability

      Data will be made available on request.

      Declaration of competing interest

      The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

      Acknowledgments

      The authors are grateful for the financial support from the National Natural Science Foundation of China (Grant no. 21971173 , 22001185 , 22171201 ), the Project of Scientific and Technologic Infrastructure of Suzhou ( SZS201905 ), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

      Appendix A. Supplementary data

      The following is the Supplementary data to this article:

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