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Synlett 2021; 32(16): 1642-1646
DOI: 10.1055/a-1517-5895
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Modern Nickel-Catalyzed Reactions

Nickel-Catalyzed Oxidative Transamidation of Tertiary Aromatic Amines with N-Acylsaccharins

Shengzhang Liu‡
a   College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022, P. R. of China
,
Lingyun Yang‡
a   College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022, P. R. of China
,
Jiasi Tao
a   College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022, P. R. of China
,
Weijie Yu
a   College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022, P. R. of China
,
Tao Wang∗
a   College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022, P. R. of China
b   National Research Center for Carbohydrate Synthesis, Jiangxi Province’s Key Laboratory of Chemical Biology, Jiangxi Normal University, Nanchang, Jiangxi 330022, P. R. of China
,
Junkai Fu  ∗
a   College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022, P. R. of China
b   National Research Center for Carbohydrate Synthesis, Jiangxi Province’s Key Laboratory of Chemical Biology, Jiangxi Normal University, Nanchang, Jiangxi 330022, P. R. of China
› Author AffiliationsWe gratefully acknowledge financial support from the National Natural Science Foundation of China (21762025, 21562026) and the Key Projects of Natural Science Foundation of Jiangxi Province (20192ACBL20026).
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Abstract

The use of tertiary amines as surrogates for secondary amines has prominent advantages in terms of stabilization and ease of handling. A Ni-catalyzed transamidation of N-acylsaccharins with tertiary aromatic amines is reported. By using tert-butyl hydroperoxide as the terminal oxidant, this reaction permits selective cleavage of the C(sp3)–N bonds of unsymmetrical tertiary aromatic amines depending on the sizes of the alkyl substituents.

Key words

transamidation - nickel catalysis - amides - tertiary amines - C–N bond cleavage

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1517-5895.
  • Supporting Information


Publication History

Received: 30 April 2021

Accepted after revision: 25 May 2021

Accepted Manuscript online:
25 May 2021

Article published online:
09 June 2021

© 2021. Thieme. All rights reserved

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  • References and Notes

    • 1a The Amide Linkage: Structural Significance in Chemistry, Biochemistry, and Materials Science. Greenberg A, Breneman CM, Liebman JF. Wiley-Interscience; 2000:
      Google Scholar
    • 1b Sewald N, Jakubke H.-D. Peptides: Chemistry and Biology . Wiley-VCH; Weinheim: 2002
      Google Scholar
    • 1c Kaspar AA, Reichert JM. Drug Discovery Today 2013; 18: 807
      CrossrefPubMed
    • 1d Winnacker M, Rieger B. Macromol. Rapid Commun. 2016; 37: 1391
      CrossrefPubMed
    • 2a Pattabiraman VR, Bode JW. Nature 2011; 480: 471
    • 2b Valeur E, Bradley M. Chem. Soc. Rev. 2009; 38: 606
      CrossrefPubMed
    • 2c Allen CL, Williams JM. J. Chem. Soc. Rev. 2011; 40: 3405
      CrossrefPubMed
    • 2d Massolo E, Pirola M, Benaglia M. Eur. J. Org. Chem. 2020; 2020: 4641
      Crossref
  • 3 Lundberg H, Tinnis F, Selander N, Adolfsson H. Chem. Soc. Rev. 2014; 43: 2714
    CrossrefPubMed
    • 4a Han S.-Y, Kim YA. Tetrahedron 2004; 60: 2447
      Crossref
    • 4b El-Faham A, Albericio F. Chem. Rev. 2011; 111: 6557
      CrossrefPubMed
    • 5a Gonzalez-Rosende ME, Castillo E, Lasri J, Sepulveda-Arques J. Prog. React. Kinet. Mech. 2004; 29: 311
      Crossref
    • 5b Lanigan RM, Sheppard TD. Eur. J. Org. Chem. 2013; 2013: 7453
      Crossref
    • 5c de Figueiredo RM, Suppo JS, Campagne J.-M. Chem. Rev. 2016; 116: 12029
      CrossrefPubMed
    • 6a Kemnitz CR, Loewen MJ. J. Am. Chem. Soc. 2007; 129: 2521
      CrossrefPubMed
    • 6b Mujika JI, Matxain JM, Eriksson LA, Lopez X. Chem. Eur. J. 2006; 12: 7215
      CrossrefPubMed
    • 7a Kirby AJ, Komarov IV, Wothers PD, Feeder N. Angew. Chem. Int. Ed. 1998; 37: 785
      CrossrefPubMed
    • 7b Kirby AJ, Komarov IV, Feeder N. J. Am. Chem. Soc. 1998; 120: 7101
      Crossref
  • 8 Tani K, Stoltz BM. Nature 2006; 441: 731
    CrossrefPubMed
  • 9 For a selected review, see: Liu, C.; Szostak, M. Chem. Eur. J. 2017, 23, 7157; and references cited therein.
    • 10a Kaiser D, Bauer A, Lemmerer M, Maulide N. Chem. Soc. Rev. 2018; 47: 7899
      CrossrefPubMed
    • 10b Adachi S, Kumagai N, Shibasaki M. Tetrahedron Lett. 2018; 59: 1147
      Crossref
    • 10c Chaudhari MB, Gnanaprakasam B. Chem. Asian J. 2019; 14: 76
      CrossrefPubMed
    • 10d Li G, Ma S, Szostak M. Trends Chem. 2020; 2: 914
    • 10e Li G, Szostak M. Chem. Rec. 2020; 20: 649
      CrossrefPubMed
  • 12 Hie L, Fine Nathel NF, Shah TK, Baker EL, Hong X, Yang Y.-F, Liu P, Houk KN, Garg NK. Nature 2015; 524: 79
    • 13a Li G, Szostak M. Synthesis 2020; 52: 2579
      Article in Thieme Connect
    • 13b Liu Y, Shi S, Achtenhagen M, Liu R, Szostak M. Org. Lett. 2017; 19: 1614
      CrossrefPubMed
    • 13c Meng G, Lei P, Szostak M. Org. Lett. 2017; 19: 2158
      CrossrefPubMed
    • 13d Li G, Szostak M. Nat. Commun. 2018; 9: 4165
    • 13e Li G, Ji C.-L, Hong X, Szostak M. J. Am. Chem. Soc. 2019; 141: 11161
      CrossrefPubMed
    • 14a Yu S, Shin T, Zhang M, Xia Y, Kim H, Lee S. Org. Lett. 2018; 20: 7563
      CrossrefPubMed
    • 14b Yang D, Shin T, Kim H, Lee S. Org. Biomol. Chem. 2020; 18: 6053
      CrossrefPubMed
    • 14c Chen J, Xia Y, Lee S. Org. Lett. 2020; 22: 3504
      CrossrefPubMed
    • 15a Baker EL, Yamano MM, Zhou Y, Anthony SM, Garg NK. Nat. Commun. 2016; 7: 11554
    • 15b Dander JE, Baker EL, Garg NK. Chem. Sci. 2017; 8: 6433
      CrossrefPubMed
    • 16a Verho O, Lati MP, Oschmann M. J. Org. Chem. 2018; 83: 4464
      CrossrefPubMed
    • 16b Mishra A, Singh S, Srivastava V. Asian J. Org. Chem. 2018; 7: 1600
      Crossref
    • 16c Mishra A, Chauhan S, Verma P, Singh S, Srivastava V. Asian J. Org. Chem. 2019; 8: 853
      Crossref
    • 16d Xiong L, Deng R, Liu T, Luo Z, Wang Z, Zhu X.-F, Wang H, Zeng Z. Adv. Synth. Catal. 2019; 361: 5383
      Crossref
    • 16e Subramani M, Rajendran SK. Eur. J. Org. Chem. 2019; 2019: 3677
      Crossref
    • 16f Sureshbabu P, Azeez S, Chaudhary P, Kandasamy J. Org. Biomol. Chem. 2019; 17: 845
      CrossrefPubMed

      For selected reviews, see:
    • 17a Ouyang K, Hao W, Zhang W.-X, Xi Z. Chem. Rev. 2015; 115: 12045
      CrossrefPubMed
    • 17b Wang Q, Su Y, Li L, Huang H. Chem. Soc. Rev. 2016; 45: 1257
      CrossrefPubMed
    • 17c García-Cárceles J, Bahou KA, Bower JF. ACS Catal. 2020; 10: 12738 ; and references cited therein
      Crossref

      For selected examples on C–N bond cleavage of tertiary amines, see:
    • 18a Shi R, Lu L, Zhang H, Chen B, Sha Y, Liu C, Lei A. Angew. Chem. Int. Ed. 2013; 52: 10582
      CrossrefPubMed
    • 18b Chen X, Chen T, Li Q, Zhou Y, Han L.-B, Yin S.-F. Chem. Eur. J. 2014; 20: 12234
      CrossrefPubMed
    • 18c Mane RS, Bhanage BM. J. Org. Chem. 2016; 81: 4974
      CrossrefPubMed
    • 18d Lai JL, Chang LM, Yuan GQ. Org. Lett. 2016; 18: 3194
      CrossrefPubMed
    • 18e Mane RS, Bhanage BM. Asian J. Org. Chem. 2018; 7: 160
      Crossref
  • 19 Idris MA, Lee S. Org. Chem. Front. 2020; 7: 2737
    Crossref
    • 20a Dander JE, Garg NK. ACS Catal. 2017; 7: 1413
      CrossrefPubMed
    • 20b Boit T, Bulger AS, Dander JE, Garg NK. ACS Catal. 2020; 10: 12109
      CrossrefPubMed
    • 21a Liu C, Meng G, Liu Y, Liu R, Lalancette R, Szostak R, Szostak M. Org. Lett. 2016; 18: 4194
      CrossrefPubMed
    • 21b Karthik S, Gandhi T. Org. Lett. 2017; 19: 5486
      CrossrefPubMed
  • 22 N-Methyl-N-phenylbenzamide (3a): Typical Procedure A 20 mL standard Schlenk tube equipped with a stirrer bar was charged with N-benzoylsaccharin (1a; 51.4 mg, 0.2 mmol, 1.0 equiv) and Ni(OTf)2 (3.6 mg, 0.02 mmol, 0.10 equiv) under N2. TBHP (28.8 μL, 0.3 mmol, 1.5 equiv), N,N-dimethylaniline (2a; 30.4 μL, 0.22 mmol, 1.1 equiv), and anhyd 1,4-dioxane (3.0 mL) were added with vigorous stirring at rt. The mixture was heated at 100 °C in an oil bath for 12 h then cooled to rt. H2O was added and the resulting mixture was poured into a separatory funnel and extracted with EtOAc. The organic layer was dried (MgSO4), filtered, and concentrated under a vacuum. The crude product was purified by column chromatography [silica gel, hexane–EtOAc (20:1)] to give a yellow oily liquid; yield: 32.1 mg (76%). 1H NMR (400 MHz, CDCl3): δ = 7.30–7.28 (m, 2 H), 7.20–7.15 (m, 3 H), 7.13–7.06 (m, 3 H), 7.01 (d, J = 7.6 Hz, 2 H), 3.46 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 170.4, 144.7, 135.8, 129.4, 128.9, 128.5, 127.5, 126.7, 126.3, 38.2. HRMS (ESI-TOF): m/z [M + Na]+ calcd for C14H13NNaO: 234.0895; found: 234.0898.
  • 23 Meng G, Szostak M. Eur. J. Org. Chem. 2018; 2018: 2352
    Crossref
    • 24a Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
      CrossrefPubMed
    • 24b Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
      CrossrefPubMed
    • 24c Berger R, Resnati G, Metrangolo P, Weber E, Hulliger J. Chem. Soc. Rev. 2011; 40: 3496
      CrossrefPubMed
  • 25 Dai F, Yang Y, Gu J, Fang Z, Yang Z, Liu C, He W, Zhu N, Lu B, Guo K. ChemistrySelect 2019; 4: 3500
    Crossref