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DOI: 10.1055/a-2034-9427
Synthesis of a Water-Soluble Tridentate (Dimethylamino)ethyl Cu(I)/Cu(II)-Ligand
This work was supported by the Deutsche Forschungsgemeinschaft (GRK 2158) and the Jürgen Manchot Foundation, Düsseldorf (scholarship to T.M.W.). We also thank Heinrich Heine University Düsseldorf and the Forschungszentrum Jülich GmbH for their ongoing support.
Dedicated to A. Stephen K. Hashmi on the occasion of his 60th birthday
Abstract
Copper-catalyzed alkyne azide click chemistry (CuAAC) plays an important role in drug development and labeling of biological materials. Stabilizing ligands prevent Cu(I)-species from oxidation, increases the solubility of copper, and increases the acceleration of the catalyzed process. In this context, we report on the synthesis of a tris-amine tridentate Cu-ligand (TDETA), with terminal (dimethylamino)ethyl-substitution, which can be legally synthesized as a replacement of toxic nitrogen mustard HN3 as an intermediate and is a scalable alternative to the previously found amine ligand DTEA. The class II ligand TDETA exhibits excellent solubility properties in organic solvents and aqueous solutions, outcompetes the commercial class I ligands THPTA and TBTA for a broad range of azide and alkyne combinations using Cu(I)- and Cu(II)-species, and was shown to be recoverable in a yield of 80%.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2034-9427.
- Supporting Information
Publication History
Received: 22 November 2022
Accepted after revision: 14 February 2023
Accepted Manuscript online:
14 February 2023
Article published online:
22 March 2023
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References
- 1a Rostovtsev VV, Green LG, Fokin VV, Sharpless KB. Angew. Chem. Int. Ed. 2002; 41: 2596
- 1b Huisgen R. Angew. Chem., Int. Ed. Engl. 1963; 2: 565
- 2a Tornøe CW, Christensen C, Meldal M. J. Org. Chem. 2002; 67: 3057
- 2b Kolb HC, Sharpless KB. Drug Discovery Today 2003; 8: 1128
- 2c Dumont A, Malleron A, Awwad M, Dukan S, Vauzeilles B. Angew. Chem. Int. Ed. 2012; 51: 3143
- 3 Brotherton WS, Michaels HA, Simmons JT, Clark RJ, Dalal NS, Zhu L. Org. Lett. 2009; 11: 4954
- 4a Chan TR, Hilgraf R, Sharpless KB, Fokin VV. Org. Lett. 2004; 6: 2853
- 4b Neumann S, Biewend M, Rana S, Binder WH. Macromol. Rapid Commun. 2020; 41: 1900359
- 5 Hein JE, Fokin VV. Chem. Soc. Rev. 2010; 39: 1302
- 6a Wang W, Hong S, Tran A, Jiang H, Triano R, Liu Y, Chen X, Wu P. Chem. Asian J. 2011; 6: 2796
- 6b Michaels HA, Zhu L. Chem. Asian J. 2011; 6: 2825
- 6c Besanceney-Webler C, Jiang H, Zheng T, Feng L, Soriano del Amo D, Wang W, Klivansky LM, Marlow FL, Liu Y, Wu P. Angew. Chem. Int. Ed. 2011; 50: 8051
- 6d Sun L, Gai Y, Anderson CJ, Zeng D. Chem. Commun. 2015; 51: 17072
- 6e Gonzalez-Lainez M, Gallegos M, Munarriz J, Azpiroz R, Passarelli V, Jiménez MV, Pérez-Torrente JJ. Organometallics 2022; 41: 2154
- 6f Guo S, Lim MH, Huynh HV. Organometallics 2013; 32: 7225
- 7 Astruc D, Wang D, Deraedt C, Liang L, Ciganda R, Ruiz J. Synthesis 2015; 47: 2017
- 8a Liang L, Astruc D. Coord. Chem. Rev. 2011; 255: 2933
- 8b Haldón E, Nicasio MC, Pérez PJ. Org. Biomol. Chem. 2015; 13: 9528
- 9 Soriano de Amo D, Wang W, Jiang H, Besanceney C, Yan AC, Levy M, Liu Y, Marlow FL, Wu P. J. Am. Chem. Soc. 2010; 132: 16893
- 10 Lu Q, Bai S, Chen Z, Zheng N, Feng X, Bai Y. ACS Mater. Lett. 2019; 2: 89
- 11 Diner I, Dooyema J, Gearing M, Walker LC, Seyfried NT. Bioconjugate Chem. 2017; 28: 2627
- 12 Wang D, Zhang Y, Kleiner RE. J. Am. Chem. Soc. 2020; 142: 14417
- 13 You Y, Deng Q, Wang Y, Sang Y, Li G, Pu F, Ren J, Qu X. Nat. Commun. 2022; 13: 1459
- 14 Lee W, Sarkar S, Pal R, Kim JY, Park H, Huynh PT, Bhise A, Bobba KN, Kim KI, Ha YS. ACS Appl. Bio Mater. 2021; 4: 2544
- 15a Munro NB, Talmage SS, Griffin GD, Waters LC, Watson AP, King JF, Hauschild V. Environ. Health Perspect. 1999; 107: 933
- 15b Organisation for the Prohibition of Chemical Weapons (OPCW) (accessed October 27, 2022): https://www.opcw.org
- 16a National Technical Reports Library, Basic Toxicity of 2-Chloro-N,N-dimethylethylamine Hydrochloride with Cover Letter, 1992, Accession Number: OTS0546424
- 16b Wang Q.-Q, Begum RA, Day VW, Bowman-James K. Org. Biomol. Chem. 2012; 10: 8786
- 17 Most Traded Scheduled Chemicals 2022 (OPCW) (accessed October 27, 2022): https://www.opcw.org/sites/default/files/documents/2021/12/Most%20Traded%20Scheduled%20Chemicals% 202022%20%28MTSC%29.pdf
- 18 Xiao C, Cheng Y, Zhang Y, Ding J, He C, Zhuang X, Chen X. J. Polym. Sci., Part A: Polym. Chem. 2014; 52: 671
- 19 Bernhard Y, Gigot E, Goncalves V, Moreau M, Sok N, Richard P, Decréau RA. Org. Biomol. Chem. 2016; 14: 4511
- 20 Engler AC, Bonner DK, Buss HG, Cheung EY, Hammond PT. Soft Matter 2011; 7: 5627
- 21 Kirby A, Suchý M, Brouwer A, Shuhendler A. Chem. Commun. 2019; 55: 5371
- 22 Polavarapu A, Stillabower JA, Stubblefield SG, Taylor WM, Baik M.-H. J. Org. Chem. 2012; 77: 5914
- 23 Reddy G, Song J, Mecchi MS, Johnson MS. Mutat. Res., Genet. Toxicol. Environ. Mutagen. 2010; 700: 26
- 24 Cegielska B, Kacprzak KM. Chem. Anal. (Warsaw, Pol.) 2009; 54: 807
- 25 Hong V, Presolski SI, Ma C, Finn MG. Angew. Chem. Int. Ed. 2009; 48: 9879
- 26 Presolski SI, Hong V, Cho S.-H, Finn M. J. Am. Chem. Soc. 2010; 132: 14570
- 27 TDETA is a non-IUPAC conform nomenclature and stands for Tris DimethylEthyl Triazolyl Amine.
- 28 Aqueous extraction of TDETA from organic solvents is not possible, as the ligand remains in the aqueous phase.