Benzyl Thioether Formation Merging Copper Catalysis

Overview

Journal RSC Adv

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2022 Apr 15

PMID 35425124

Authors

Bing Xu

Ying Lin

Yang Ye

Li Xu

Tian Xie

Xiang-Yang Ye

Affiliations

Soon will be listed here.

Abstract

A novel copper-catalyzed thioetherification reaction has been developed to afford benzyl thioethers in moderate to excellent yields. Under the mild and easy-to-operate conditions, a variety of thioethers are efficiently prepared from readily available benzyl alcohols (primary, secondary, and tertiary) and thiols in the presence of Cu(OTf) as the Lewis acid catalysis. This C-S bond formation protocol furnishes exceptional chemoselectivity, and the preliminary mechanism studies show that the reaction should proceed through a Lewis-acid-mediated S1-type nucleophilic attack of the carbocations formed .

Citing Articles

Access to thioethers from thiols and alcohols via homogeneous and heterogeneous catalysis.

Markwitz M, Labrzycki K, Azcune L, Landa A, Kucinski K Sci Rep. 2023; 13(1):20624.

PMID: 37996490 PMC: 10667213. DOI: 10.1038/s41598-023-47938-4.

References

Rosen B, Quasdorf K, Wilson D, Zhang N, Resmerita A, Garg N . Nickel-catalyzed cross-couplings involving carbon-oxygen bonds. Chem Rev. 2010; 111(3):1346-416. PMC: 3055945. DOI: 10.1021/cr100259t. View

Bisz E, Szostak M . Iron-Catalyzed C-O Bond Activation: Opportunity for Sustainable Catalysis. ChemSusChem. 2017; 10(20):3964-3981. DOI: 10.1002/cssc.201701287. View

Gao Y, Zhang H, Lirussi F, Garrido C, Ye X, Xie T . Dual inhibitors of histone deacetylases and other cancer-related targets: A pharmacological perspective. Biochem Pharmacol. 2020; 182:114224. DOI: 10.1016/j.bcp.2020.114224. View

Nicolaou K, Hale C, Nilewski C, Ioannidou H . Constructing molecular complexity and diversity: total synthesis of natural products of biological and medicinal importance. Chem Soc Rev. 2012; 41(15):5185-238. PMC: 3426871. DOI: 10.1039/c2cs35116a. View

Wang C, Liu J, Kong J, Zhang X . Nitronyl nitroxide monoradical TEMPO as new electrochemical label for ultrasensitive detection of nucleic acids. Anal Chim Acta. 2020; 1136:19-24. DOI: 10.1016/j.aca.2020.08.035. View

Lin D, Zhang S, Block E, Katz L . Encoding social signals in the mouse main olfactory bulb. Nature. 2005; 434(7032):470-7. DOI: 10.1038/nature03414. View

Sundararaju B, Achard M, Bruneau C . Transition metal catalyzed nucleophilic allylic substitution: activation of allylic alcohols via π-allylic species. Chem Soc Rev. 2012; 41(12):4467-83. DOI: 10.1039/c2cs35024f. View

Burckstummer H, Weissenstein A, Bialas D, Wurthner F . Synthesis and characterization of optical and redox properties of bithiophene-functionalized diketopyrrolopyrrole chromophores. J Org Chem. 2011; 76(8):2426-32. DOI: 10.1021/jo2003117. View

Watile R, Bunrit A, Margalef J, Akkarasamiyo S, Ayub R, Lagerspets E . Intramolecular substitutions of secondary and tertiary alcohols with chirality transfer by an iron(III) catalyst. Nat Commun. 2019; 10(1):3826. PMC: 6707304. DOI: 10.1038/s41467-019-11838-x. View

10.

Alvaro E, Hartwig J . Resting state and elementary steps of the coupling of aryl halides with thiols catalyzed by alkylbisphosphine complexes of palladium. J Am Chem Soc. 2009; 131(22):7858-68. PMC: 2853813. DOI: 10.1021/ja901793w. View

11.

Pronin S, Reiher C, Shenvi R . Stereoinversion of tertiary alcohols to tertiary-alkyl isonitriles and amines. Nature. 2013; 501(7466):195-9. DOI: 10.1038/nature12472. View

12.

Hu S, Hui Z, Lirussi F, Garrido C, Ye X, Xie T . Small molecule DNA-PK inhibitors as potential cancer therapy: a patent review (2010-present). Expert Opin Ther Pat. 2020; 31(5):435-452. DOI: 10.1080/13543776.2021.1866540. View

13.

Feng M, Tang B, Liang S, Jiang X . Sulfur Containing Scaffolds in Drugs: Synthesis and Application in Medicinal Chemistry. Curr Top Med Chem. 2015; 16(11):1200-16. PMC: 4877035. DOI: 10.2174/1568026615666150915111741. View

14.

Zhan Z, Yu J, Liu H, Cui Y, Yang R, Yang W . A general and efficient FeCl3-catalyzed nucleophilic substitution of propargylic alcohols. J Org Chem. 2006; 71(21):8298-301. DOI: 10.1021/jo061234p. View

15.

Zhai B, Zhang N, Han X, Li Q, Zhang M, Chen X . Molecular targets of β-elemene, a herbal extract used in traditional Chinese medicine, and its potential role in cancer therapy: A review. Biomed Pharmacother. 2019; 114:108812. DOI: 10.1016/j.biopha.2019.108812. View

16.

Yang Y, Ye Z, Zhang X, Zhou Y, Ma X, Cao H . Efficient dehydrative alkylation of thiols with alcohols catalyzed by alkyl halides. Org Biomol Chem. 2017; 15(45):9638-9642. DOI: 10.1039/c7ob02461d. View

17.

Su B, Cao Z, Shi Z . Exploration of earth-abundant transition metals (Fe, Co, and Ni) as catalysts in unreactive chemical bond activations. Acc Chem Res. 2015; 48(3):886-96. DOI: 10.1021/ar500345f. View

18.

Borthwick A . 2,5-Diketopiperazines: synthesis, reactions, medicinal chemistry, and bioactive natural products. Chem Rev. 2012; 112(7):3641-716. DOI: 10.1021/cr200398y. View

19.

Mishra A, Ma C, Bauerle P . Functional oligothiophenes: molecular design for multidimensional nanoarchitectures and their applications. Chem Rev. 2009; 109(3):1141-276. DOI: 10.1021/cr8004229. View

20.

Zhang X, Ren J, Tan S, Tan D, Lee R, Tan C . An enantioconvergent halogenophilic nucleophilic substitution (S2X) reaction. Science. 2019; 363(6425):400-404. DOI: 10.1126/science.aau7797. View