Sulfur-Phenolate Exchange As a Mild, Fast, and High-Yielding Method Toward the Synthesis of Sulfonamides

Overview

Journal Org Lett

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2023 Jan 31

PMID 36720015

Authors

Alyssa F J van den Boom

Han Zuilhof

Affiliations

Soon will be listed here.

Abstract

Sulfonamides have many important biological applications, yet their synthesis often involves long reaction times under dry and non-ambient conditions. Here we report the synthesis of a large range of sulfonamides at room temperature using 4-nitrophenyl benzylsulfonate as a starting material. Sulfonamides were prepared from a wide range of aliphatic, linear, and cyclic amines, anilines, and -methylanilines. The yields and reaction times observed here were comparable to or better than those reported previously, establishing sulfur-phenolate exchange as a viable alternative.

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References

Saupe S, Leubner S, Betz M, Klebe G, Steinmetzer T . Development of new cyclic plasmin inhibitors with excellent potency and selectivity. J Med Chem. 2013; 56(3):820-31. DOI: 10.1021/jm3012917. View

Smedley C, Homer J, Gialelis T, Barrow A, Koelln R, Moses J . Accelerated SuFEx Click Chemistry For Modular Synthesis. Angew Chem Int Ed Engl. 2021; 61(4):e202112375. PMC: 8867595. DOI: 10.1002/anie.202112375. View

Zhu J, Chen H, Guo X, Qiu X, Hu C, Chamberlin A . Synthesis, molecular modeling, and biological evaluation of novel RAD51 inhibitors. Eur J Med Chem. 2015; 96:196-208. PMC: 4433875. DOI: 10.1016/j.ejmech.2015.04.021. View

Li S, Li G, Gao B, Pujari S, Chen X, Kim H . SuFExable polymers with helical structures derived from thionyl tetrafluoride. Nat Chem. 2021; 13(9):858-867. PMC: 8713280. DOI: 10.1038/s41557-021-00726-x. View

Tomassi C, Van Nhien A, Marco-Contelles J, Balzarini J, Pannecouque C, De Clercq E . Synthesis and anti-HIV1 biological activity of novel 5''-ATSAO compounds. Bioorg Med Chem. 2008; 16(8):4733-41. DOI: 10.1016/j.bmc.2008.02.026. View

Liang D, Pujari S, Subramaniam M, Besten M, Zuilhof H . Configurationally Chiral SuFEx-Based Polymers. Angew Chem Int Ed Engl. 2021; 61(8):e202116158. PMC: 9303861. DOI: 10.1002/anie.202116158. View

Chazalette C, Supuran C, Scozzafava A . Carbonic anhydrase inhibitors: allylsulfonamide, styrene sulfonamide, N-allyl sulfonamides and some of their Si, Ge, and B derivatives. J Enzyme Inhib. 2002; 16(6):475-89. DOI: 10.1080/14756360127572. View

Tang J, Chen H, He Y, Sheng W, Bai Q, Wang H . Peptide-guided functionalization and macrocyclization of bioactive peptidosulfonamides by Pd(II)-catalyzed late-stage C-H activation. Nat Commun. 2018; 9(1):3383. PMC: 6107497. DOI: 10.1038/s41467-018-05440-w. View

Harger M . Competing sulfonylation and phosphonylation following rearrangement of an O-sulfonyl-N-phosphinoylhydroxylamine with tert-butylamine: demonstration of a phosphonamidic-sulfonic anhydride intermediate and 18O-labelling evidence on how it may be formed. Org Biomol Chem. 2003; 1(19):3390-5. DOI: 10.1039/b305510h. View

10.

Dong J, Krasnova L, Finn M, Sharpless K . Sulfur(VI) fluoride exchange (SuFEx): another good reaction for click chemistry. Angew Chem Int Ed Engl. 2014; 53(36):9430-48. DOI: 10.1002/anie.201309399. View

11.

Day J, Neill D, Xu S, Xian M . Benzothiazole Sulfinate: A Sulfinic Acid Transfer Reagent under Oxidation-Free Conditions. Org Lett. 2017; 19(14):3819-3822. PMC: 5863730. DOI: 10.1021/acs.orglett.7b01693. View

12.

Smedley C, Li G, Barrow A, Gialelis T, Giel M, Ottonello A . Diversity Oriented Clicking (DOC): Divergent Synthesis of SuFExable Pharmacophores from 2-Substituted-Alkynyl-1-Sulfonyl Fluoride (SASF) Hubs. Angew Chem Int Ed Engl. 2020; 59(30):12460-12469. PMC: 7572632. DOI: 10.1002/anie.202003219. View

13.

Rouffet M, de Oliveira C, Udi Y, Agrawal A, Sagi I, McCammon J . From sensors to silencers: quinoline- and benzimidazole-sulfonamides as inhibitors for zinc proteases. J Am Chem Soc. 2010; 132(24):8232-3. PMC: 2886603. DOI: 10.1021/ja101088j. View

14.

Cheng G, Wang P, Yu J . meta-C-H Arylation and Alkylation of Benzylsulfonamide Enabled by a Palladium(II)/Isoquinoline Catalyst. Angew Chem Int Ed Engl. 2017; 56(28):8183-8186. PMC: 5553125. DOI: 10.1002/anie.201704411. View

15.

Dondoni A, Marra A . SuFEx: a metal-free click ligation for multivalent biomolecules. Org Biomol Chem. 2017; 15(7):1549-1553. DOI: 10.1039/c6ob02458k. View

16.

Coburn C, Luo Y, Cui M, Wang J, Soll R, Dong J . Discovery of a pharmacologically active antagonist of the two-pore-domain potassium channel K2P9.1 (TASK-3). ChemMedChem. 2011; 7(1):123-33. DOI: 10.1002/cmdc.201100351. View

17.

Lou T, Willis M . Sulfonyl fluorides as targets and substrates in the development of new synthetic methods. Nat Rev Chem. 2023; 6(2):146-162. DOI: 10.1038/s41570-021-00352-8. View

18.

Liang D, Streefkerk D, Jordaan D, Wagemakers J, Baggerman J, Zuilhof H . Silicon-Free SuFEx Reactions of Sulfonimidoyl Fluorides: Scope, Enantioselectivity, and Mechanism. Angew Chem Int Ed Engl. 2020; 59(19):7494-7500. PMC: 7216998. DOI: 10.1002/anie.201915519. View

19.

Wei M, Liang D, Cao X, Luo W, Ma G, Liu Z . A Broad-Spectrum Catalytic Amidation of Sulfonyl Fluorides and Fluorosulfates*. Angew Chem Int Ed Engl. 2020; 60(13):7397-7404. DOI: 10.1002/anie.202013976. View

20.

Chen H, Wang L, Han J . Deacetylative Aryl Migration of Diaryliodonium Salts with C(sp)-N Bond Formation toward -Iodo -Aryl Sulfonamides. Org Lett. 2020; 22(9):3581-3585. DOI: 10.1021/acs.orglett.0c01024. View