Synthesis of a Water-Soluble Tridentate (Dimethylamino)ethyl Cu(I)/Cu(II)-Ligand

T. Moritz Weber; Jörg Pietruszka

doi:10.1055/a-2034-9427

Synthesis, Inhaltsverzeichnis

Synthesis 2023; 55(14): 2128-2133
DOI: 10.1055/a-2034-9427

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Synthesis of a Water-Soluble Tridentate (Dimethylamino)ethyl Cu(I)/Cu(II)-Ligand

T. Moritz Weber

^aInstitute of Bioorganic Chemistry, Heinrich Heine University at Forschungszentrum Jülich and Bioeconomy Science Center (BioSC), Stetternicher Forst, 52426 Jülich, Germany

,

Jörg Pietruszka ∗

^aInstitute of Bioorganic Chemistry, Heinrich Heine University at Forschungszentrum Jülich and Bioeconomy Science Center (BioSC), Stetternicher Forst, 52426 Jülich, Germany

^bInstitute of Bio- and Geosciences (IBG-1: Biotechnology), Forschungszentrum Jülich, Wilhelm-Johnen-Straße, 52428 Jülich, Germany

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Abstract

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Dedicated to A. Stephen K. Hashmi on the occasion of his 60^th 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%.

Key words

click chemistry - ligand - azide - alkyne - cycloaddition - copper

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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.

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