Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2021; 32(16): 1642-1646
DOI: 10.1055/a-1517-5895
DOI: 10.1055/a-1517-5895
cluster
Modern Nickel-Catalyzed Reactions
Nickel-Catalyzed Oxidative Transamidation of Tertiary Aromatic Amines with N-Acylsaccharins
We 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).
![](https://www.thieme-connect.de/media/synlett/202116/lookinside/thumbnails/st-2021-k0174-c_10-1055_a-1517-5895-1.jpg)
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.
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
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References and Notes
- 1a The Amide Linkage: Structural Significance in Chemistry, Biochemistry, and Materials Science. Greenberg A, Breneman CM, Liebman JF. Wiley-Interscience; 2000:
- 1b Sewald N, Jakubke H.-D. Peptides: Chemistry and Biology . Wiley-VCH; Weinheim: 2002
- 1c Kaspar AA, Reichert JM. Drug Discovery Today 2013; 18: 807
- 1d Winnacker M, Rieger B. Macromol. Rapid Commun. 2016; 37: 1391
-
2a
Pattabiraman VR,
Bode JW.
Nature 2011; 480: 471
- 2b Valeur E, Bradley M. Chem. Soc. Rev. 2009; 38: 606
- 2c Allen CL, Williams JM. J. Chem. Soc. Rev. 2011; 40: 3405
- 2d Massolo E, Pirola M, Benaglia M. Eur. J. Org. Chem. 2020; 2020: 4641
- 3 Lundberg H, Tinnis F, Selander N, Adolfsson H. Chem. Soc. Rev. 2014; 43: 2714
- 4a Han S.-Y, Kim YA. Tetrahedron 2004; 60: 2447
- 4b El-Faham A, Albericio F. Chem. Rev. 2011; 111: 6557
- 5a Gonzalez-Rosende ME, Castillo E, Lasri J, Sepulveda-Arques J. Prog. React. Kinet. Mech. 2004; 29: 311
- 5b Lanigan RM, Sheppard TD. Eur. J. Org. Chem. 2013; 2013: 7453
- 5c de Figueiredo RM, Suppo JS, Campagne J.-M. Chem. Rev. 2016; 116: 12029
- 6a Kemnitz CR, Loewen MJ. J. Am. Chem. Soc. 2007; 129: 2521
- 6b Mujika JI, Matxain JM, Eriksson LA, Lopez X. Chem. Eur. J. 2006; 12: 7215
- 7a Kirby AJ, Komarov IV, Wothers PD, Feeder N. Angew. Chem. Int. Ed. 1998; 37: 785
- 7b Kirby AJ, Komarov IV, Feeder N. J. Am. Chem. Soc. 1998; 120: 7101
- 8 Tani K, Stoltz BM. Nature 2006; 441: 731
-
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
- 10b Adachi S, Kumagai N, Shibasaki M. Tetrahedron Lett. 2018; 59: 1147
- 10c Chaudhari MB, Gnanaprakasam B. Chem. Asian J. 2019; 14: 76
-
10d
Li G,
Ma S,
Szostak M.
Trends Chem. 2020; 2: 914
- 10e Li G, Szostak M. Chem. Rec. 2020; 20: 649
- 11a Meng G, Szostak M. Org. Lett. 2015; 17: 4364
- 11b Meng G, Szostak M. Angew. Chem. Int. Ed. 2015; 54: 14518
-
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
- 13b Liu Y, Shi S, Achtenhagen M, Liu R, Szostak M. Org. Lett. 2017; 19: 1614
- 13c Meng G, Lei P, Szostak M. Org. Lett. 2017; 19: 2158
-
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
- 14a Yu S, Shin T, Zhang M, Xia Y, Kim H, Lee S. Org. Lett. 2018; 20: 7563
- 14b Yang D, Shin T, Kim H, Lee S. Org. Biomol. Chem. 2020; 18: 6053
- 14c Chen J, Xia Y, Lee S. Org. Lett. 2020; 22: 3504
-
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
- 16a Verho O, Lati MP, Oschmann M. J. Org. Chem. 2018; 83: 4464
- 16b Mishra A, Singh S, Srivastava V. Asian J. Org. Chem. 2018; 7: 1600
- 16c Mishra A, Chauhan S, Verma P, Singh S, Srivastava V. Asian J. Org. Chem. 2019; 8: 853
- 16d Xiong L, Deng R, Liu T, Luo Z, Wang Z, Zhu X.-F, Wang H, Zeng Z. Adv. Synth. Catal. 2019; 361: 5383
- 16e Subramani M, Rajendran SK. Eur. J. Org. Chem. 2019; 2019: 3677
- 16f Sureshbabu P, Azeez S, Chaudhary P, Kandasamy J. Org. Biomol. Chem. 2019; 17: 845
- 17a Ouyang K, Hao W, Zhang W.-X, Xi Z. Chem. Rev. 2015; 115: 12045
- 17b Wang Q, Su Y, Li L, Huang H. Chem. Soc. Rev. 2016; 45: 1257
- 17c García-Cárceles J, Bahou KA, Bower JF. ACS Catal. 2020; 10: 12738 ; and references cited therein
- 18a Shi R, Lu L, Zhang H, Chen B, Sha Y, Liu C, Lei A. Angew. Chem. Int. Ed. 2013; 52: 10582
- 18b Chen X, Chen T, Li Q, Zhou Y, Han L.-B, Yin S.-F. Chem. Eur. J. 2014; 20: 12234
- 18c Mane RS, Bhanage BM. J. Org. Chem. 2016; 81: 4974
- 18d Lai JL, Chang LM, Yuan GQ. Org. Lett. 2016; 18: 3194
- 18e Mane RS, Bhanage BM. Asian J. Org. Chem. 2018; 7: 160
- 19 Idris MA, Lee S. Org. Chem. Front. 2020; 7: 2737
- 20a Dander JE, Garg NK. ACS Catal. 2017; 7: 1413
- 20b Boit T, Bulger AS, Dander JE, Garg NK. ACS Catal. 2020; 10: 12109
- 21a Liu C, Meng G, Liu Y, Liu R, Lalancette R, Szostak R, Szostak M. Org. Lett. 2016; 18: 4194
- 21b Karthik S, Gandhi T. Org. Lett. 2017; 19: 5486
-
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
- 24a Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
- 24b Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
- 24c Berger R, Resnati G, Metrangolo P, Weber E, Hulliger J. Chem. Soc. Rev. 2011; 40: 3496
- 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
For selected reviews, see:
For selected examples on C–N bond cleavage of tertiary amines, see: