Synlett 2021; 32(15): 1531-1536
DOI: 10.1055/s-0040-1707301
cluster
Modern Nickel-Catalyzed Reactions

C(sp3)–H Bond Acylation with N-Acyl Imides under Photoredox/ Nickel Dual Catalysis

Taline Kerackian
a   Univ Lyon, Université Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, UMR 5246 du CNRS, 1 rue Victor Grignard, 69100 Villeurbanne, France   Email: abderrahmane.amgoune@univ-lyon1.fr
,
Antonio Reina
a   Univ Lyon, Université Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, UMR 5246 du CNRS, 1 rue Victor Grignard, 69100 Villeurbanne, France   Email: abderrahmane.amgoune@univ-lyon1.fr
,
Tetiana Krachko
a   Univ Lyon, Université Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, UMR 5246 du CNRS, 1 rue Victor Grignard, 69100 Villeurbanne, France   Email: abderrahmane.amgoune@univ-lyon1.fr
,
Hugo Boddaert
a   Univ Lyon, Université Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, UMR 5246 du CNRS, 1 rue Victor Grignard, 69100 Villeurbanne, France   Email: abderrahmane.amgoune@univ-lyon1.fr
,
Didier Bouyssi
a   Univ Lyon, Université Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, UMR 5246 du CNRS, 1 rue Victor Grignard, 69100 Villeurbanne, France   Email: abderrahmane.amgoune@univ-lyon1.fr
,
Nuno Monteiro
a   Univ Lyon, Université Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, UMR 5246 du CNRS, 1 rue Victor Grignard, 69100 Villeurbanne, France   Email: abderrahmane.amgoune@univ-lyon1.fr
,
a   Univ Lyon, Université Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, UMR 5246 du CNRS, 1 rue Victor Grignard, 69100 Villeurbanne, France   Email: abderrahmane.amgoune@univ-lyon1.fr
b   Institut Universitaire de France (IUF), 1 rue Descartes, 75231 Paris, France
› Author Affiliations
Financial support from the Université de Lyon, IDEXLYON project (ANR-16_IDEX-0005) and the Agence Nationale de la Recherche (ANR-JCJC-2016-CHAUCACAO) is gratefully acknowledged. T.K. thanks the French Ministry of Higher Education and Research for a doctoral fellowship.


Abstract

A novel Ni/photoredox-catalyzed acylation of aliphatic substrates, including simple alkanes and dialkyl ethers, has been developed. The method combines C–N bond activation of amides with a radical relay mechanism involving hydrogen-atom transfer. The protocol is operationally simple, employs bench-stable N-acyl imides as acyl-transfer reagents, and permits facile access to alkyl ketones under very mild conditions.

Supporting Information



Publication History

Received: 31 July 2020

Accepted after revision: 31 August 2020

Article published online:
08 October 2020

© 2020. Thieme. All rights reserved

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  • References and Notes

  • 1 Siegel H, Eggersdorfer M. In Ullmann's Encyclopedia of Industrial Chemistry . Bohnet M. Wiley-VCH; Weinheim: 2000. DOI: 10.1002/14356007.a15_077

    • For reviews, see:
    • 2a Twilton J, Le C, Zhang P, Shaw MH, Evans RW, MacMillan DW. C. Nat. Rev. Chem. 2017; 1: 0052
    • 2b Milligan JA, Phelan JP, Badir SO, Molander GA. Angew. Chem. Int. Ed. 2019; 58: 6152
    • 2c Zhu C, Yue H, Chu L, Rueping M. Chem. Sci. 2020; 11: 4051

      For overviews of recent photoredox methods for ketone synthesis, see:
    • 3a Chalotra N, Sultan S, Shah BA. Asian J. Org. Chem. 2020; 9: 863
    • 3b Lee KN, Ngai M.-Y. Chem. Commun. 2017; 53: 13093

      For reviews of metal-catalyzed acylative cross-coupling reactions for ketone synthesis, see:
    • 4a Dieter RK. Tetrahedron 1999; 55: 4177
    • 4b Gooßen LJ, Rodriguez N, Gooßen K. Angew. Chem. Int. Ed. 2008; 47: 3100
    • 4c Buchspies J, Szostak M. Catalysts 2019; 9: 53
    • 4d Ogiwara Y, Sakai N. Angew. Chem. Int. Ed. 2020; 59: 574

      For general illustrations of the reactivity of twisted amides as acylating reagents, see:
    • 5a Meng G, Shi S, Szostak M. Synlett 2016; 2530
    • 5b Pace V, Holzer W, Meng G, Shi S, Lalancette R, Szostak R, Szostak M. Chem. Eur. J. 2016; 22: 14494
    • 5c Shi S, Szostak M. Synthesis 2017; 49: 3602
    • 5d Osumi Y, Liu C, Szostak M. Org. Biomol. Chem. 2017; 15: 8867
    • 5e Meng G, Szostak M. Eur. J. Org. Chem. 2018; 2018: 2352
    • 5f Szostak R, Szostak M. Org. Lett. 2018; 20: 1342
    • 5g Liu C, Szostak M. Org. Biomol. Chem. 2018; 16: 7998

      For selected examples, see:
    • 6a Simmons BJ, Weires NA, Dander JE, Garg NK. ACS Catal. 2016; 6: 3176
    • 6b Liu X, Hsiao C.-C, Guo L, Rueping M. Org. Lett. 2018; 20: 2976
    • 6c Yu C.-G, Matsuo Y. Org. Lett. 2020; 22: 950
    • 6d Zhuo J, Zhang Y, Li Z, Li C. ACS Catal. 2020; 10: 3895

    • For an example of aryl ketone synthesis, see:
    • 6e Ni S, Zhang W, Mei H, Han J, Pan Y. Org. Lett. 2017; 19: 2536
  • 7 Amani J, Alam R, Badir S, Molander GA. Org. Lett. 2017; 19: 2426

    • For similar strategies making use of acyl chlorides or carboxylic acids as electrophilic partners, see:
    • 8a Amani J, Sodagar E, Molander GA. Org. Lett. 2016; 18: 732
    • 8b Amani J, Molander GA. J. Org. Chem. 2017; 82: 1856
    • 8c Amani J, Molander GA. Org. Lett. 2017; 19: 3612
    • 8d Levernier E, Corcé V, Rakotoarison L.-M, Smith A, Zhang M, Ognier S, Tatoulian M, Ollivier C, Fensterbank L. Org. Chem. Front. 2019; 6: 1378
  • 9 For a review of acylative cross-electrophile coupling reactions, see: Moragas, T.; Correa, A.; Martin, R. Chem. Eur. J. 2014, 20, 8242. For rare examples of cross-electrophile coupling reactions employing amides, see refs. 6c–e.
  • 10 Kerackian T, Reina A, Bouyssi D, Monteiro N, Amgoune A. Org. Lett. 2020; 2240

    • For seminal papers on HAT-mediated Ni/photoredox cross-coupling reactions, see:
    • 11a Zuo Z, Ahneman DT, Chu L, Terrett JA, Doyle AG, MacMillan DW. C. Science 2014; 345: 437
    • 11b Shaw MH, Shurtleff VW, Terrett JA, Cuthbertson JD, MacMillan DW. C. Science 2016; 352: 1304

    • For general reviews of HAT-mediated photocatalytic reactions, see:
    • 11c Capaldo L, Ravelli D. Eur. J. Org. Chem. 2017; 2056
    • 11d Capaldo L, Lafayette Quadri L, Ravelli D. Green Chem. 2020; 22: 3376

      For selected papers on acylation reactions based on HAT-mediated Ni/photoredox cross-coupling reactions, see:
    • 12a Joe CL, Doyle AG. Angew. Chem. Int. Ed. 2016; 55: 4040
    • 12b Sun Z, Kumagai N, Shibasaki M. Org. Lett. 2017; 19: 3727
    • 12c Kang B, Hong SH. Chem. Sci. 2017; 8: 6613
    • 12d Ackerman LK. G, Martinez Alvarado JI, Doyle AG. J. Am. Chem. Soc. 2018; 140: 14059
    • 12e Schirmer TE, Wimmer A, Weinzierl FW. C, König B. Chem. Commun. 2019; 55: 10796
    • 12f Krach PE, Dewanji A, Yuan T, Rueping M. Chem. Commun. 2020; 56: 6082
    • 13a Heitz DR, Tellis JC, Molander GA. J. Am. Chem. Soc. 2016; 138: 12715
    • 13b Shields BJ, Doyle AG. J. Am. Chem. Soc. 2016; 138: 12719
    • 13c Nielsen MK, Shields BJ, Liu J, Williams MJ, Zacuto MJ, Doyle AG. Angew. Chem. Int. Ed. 2017; 56: 7191

    • For other illustrative examples, see:
    • 13d Huang L, Rueping M. Angew. Chem. Int. Ed. 2018; 57: 10333
    • 13e Shen Y, Gu Y, Martin R. J. Am. Chem. Soc. 2018; 140: 12200
    • 13f Cheng X, Lu H, Lu Z. Nat. Commun. 2019; 10: 3549
    • 13g Santos MS, Corrêa AG, Paixão MW, König B. Adv. Synth. Catal. 2020; 2367

    • For examples involving carbonyl-type electrophiles, see refs. 12b and 12d
  • 14 Doyle showed that external sources of chlorine atom such as TBACl can be used to cross-couple electrophiles that do not contain chloride (e.g., aryl triflates, bromides, or iodides); see refs. 13b and 13c.
    • 15a Hwang SJ, Powers DC, Maher AG, Anderson BL, Hadt RG, Zheng S.-L, Chen S.-Y, Nocera DG. J. Am. Chem. Soc. 2015; 137: 6472
    • 15b Hwang SJ, Anderson BL, Powers DC, Maher AG, Hadt RG, Nocera DG. Organometallics 2015; 34: 4766
  • 16 See the Supporting Information for more details.
  • 17 Cyclohexyl(phenyl)methanone (3a); Typical Procedure A In an argon-filled glovebox, a 10 mL Schlenk tube equipped with a magnetic stirrer bar was charged with Ir{[dF(CF3)ppy]2(dtbbpy)}PF6 (0.003 mmol, 3.2 mg), [Ni(dtbbpy)(H2O)4]Cl2 (0.024 mmol, 11.2 mg), K3PO4 (1.2 mmol, 254 mg), Na2WO4·2 H2O (0.6 mmol, 200 mg), LiCl (0.6 mmol, 25 mg), N-benzoylsuccinimide (0.6 mmol, 122 mg), cyclohexane (3.0 mmol, 325 μL), and anhyd benzene (6 mL). The sealed vessel was taken out of the glovebox, and the stirred mixture was irradiated by a 40 W blue LED Kessil lamp (455 nm) for 24 hours at RT. To remove solid residues, the mixture was filtered through a short pad of Celite with CH2Cl2 as the eluent. The volatiles were removed under vacuum and the crude residue was purified by column chromatography [silica gel, cyclohexane–EtOAc (10:1)] to give a colorless oil; yield: 60 mg (53%). The 1H NMR and 13C NMR spectra were consistent with values reported in the literature.8b
  • 18 Phenyl(tetrahydrofuran-2-yl)methanone (3i); Typical Procedure B On the bench top, an 8 mL scintillation vial equipped with a magnetic stirrer bar was charged with Ir{[dF(CF3)ppy]2(dtbbpy)}PF6 (0.008 mmol, 9 mg), [Ni(dtbbpy)(H2O)4]Cl2 (0.04 mmol, 18.7 mg), K3PO4 (0.6 mmol, 127 mg), LiCl (0.4 mmol, 17 mg), N-benzoylsuccinimide (0.4 mmol, 81.3 mg), and anhyd THF (3.2 mL, 0.125 M). The vial was sparged with argon then sealed, and the stirred mixture was irradiated by a 30 W blue LED lamp (450 nm; EvoluChem PhotoRedOx Box device) for 24 h at RT. To remove solid residues, the mixture was filtered through a short pad of Celite with CH2Cl2 as eluent. The volatiles were removed under vacuum and the crude residue was purified by column chromatography [silica gel cyclohexane–EtOAc (10:1)] to give a colorless oil; yield: 37.5 mg (53%). The 1H NMR and 13C NMR spectra were consistent with the values reported in the literature.12b
  • 19 CCDC 2018793 contains the supplementary crystallographic data for complex III. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
  • 20 A single precedent has been reported for the formation of an acyl nickel(II) complex by amide C−N bond activation in which, after a ligand exchange between the transient amidate complex and a chloride ion, a Ni(II) chloride complex was isolated and structurally characterized; see: Hu J, Zhao Y, Liu J, Zhang Y, Shi Z. Angew. Chem. Int. Ed. 2016; 55: 8718
  • 21 The formation of alkyl ketones deriving from a decarbonylative process with ethyl chloroformate has been recently reported; see: Shi R, Hu X. Angew. Chem. Int. Ed. 2019; 58: 7454
  • 22 For the coupling of N-benzoylsuccinimide (1a) with cyclohexane, 4a could also be formed by direct attack of the cyclohexyl radical on benzene. See the Supporting Information for more details.
  • 23 Mohadjer Beromi M, Brudvig GW, Hazari N, Lant HM. C, Mercado BQ. Angew. Chem. Int. Ed. 2019; 58: 6094
  • 24 During the final stage of the preparation of this manuscript, a similar protocol for the acylation of C(sp3)–H bonds with N-acylsuccinimides was published, see: Lee GS, Won J, Choi S, Baik M.-H, Hong SH. Angew. Chem. Int. Ed. 2020; 59: 16933