Green Synthesis of Aryl Thioethers through Cu-catalysed C-S Coupling of Thiols and Aryl Boronic Acids in Water

Abstract

An efficient, practical, highly selective and environmentally benign method is reported for the synthesis of aryl thioethers via the coupling of thiols with aryl boronic acids in the presence of NaOH and a catalytic amount of CuSO₄ at 130 °C using water as a green solvent. The products were obtained in moderate to excellent yields; more importantly, the use of toxic ligands and solvents was avoided. A broad range of aryl boronic acids and scalable processes make this methodology valuable and versatile for the synthesis of a broad range of aryl sulfides.

Keywords

green synthesis / Cu-catalysed C-S coupling / aryl boronic acids / water solvent / aryl thioether

References

[1] Johannesson P, Lindeberg G, Johansson A, et al. Vinyl Sulfide Cyclized Analogues of Angiotensin II with High Affinity and Full Agonist Activity at the AT1 Receptor [J]. J. Med. Chem., 2002, 459: 1767-1777.

[2] Dvorak CA, Schmitz WD, Poon DJ, et al. The Synthesis of Streptogramin Antibiotics:(-)-Gr Iseoviridin and Its C-8Epimer [J]. Angew. Chem., 2000, 112(9): 1730-1732.

[3] Lu GP, Chen F, Cai C. Thiourea in the Construction of C-S Bonds as Part of an Undergraduate Organic Chemistry Laboratory Course [J]. J. Chem. Educ., 2017, 94(2): 244-247.

[4] Singh R, Raghuvanshi DS, Singh KN. Regioselective Hydrothiolation of Alkynes by Sulfonyl Hydrazides Using Organic Ionic Base-Brønsted Acid [J]. Org. Lett., 2013, 15(16): 4202-4205.

[5] Beletskaya IP, Ananikov VP. Transition-Metal-Catalyzed C-S, C-Se, and C-Te Bond Formation via Cross-Coupling and Atom-Economic Addition Reactions [J]. Chem. Rev., 2011, 111(3): 1596

[6] Dang P, Zheng Z, Liang Y. J. Org. Chem., 2017, 82: 2263-2268.

[7] Liu G, Kong L, Shen J, et al. A regio- and Stereoselective Entry to (Z)- ß-halo Alkenyl Sulfides and Their Applications to Access Stereodefined Trisubstituted Alkenes [J]. Org. Biomol. Chem., 2014, 12(14): 2310-2321.

[8] Liao Y, Chen S, Jiang P, et al. Stereoselective Formation of Z- or E-Vinyl Thioethers from Arylthiols and Acetylenes under Transition-Metal-Free Conditions [J]. Eur. J. Org. Chem., 2013, 2013(30): 6878-6885.

[9] Lin C, Li D, Wang B, et al. Direct ortho-Thiolation of Arenes and Alkenes by Nickel Catalysis [J]. Org. Lett., 2015, 17(5): 1328-1331.

[10] Sarma R, Rajesh N, Prajapat D. Indium(III) Catalysed Substrate Selective Hydrothiolation of Terminal Alkynes [J]. Chem. Commun., 2012, 48(33): 4014-4016.

[11] Li Q, Dong T, Liu X, et al. A Bioorthogonal Ligation Enabled by Click Cycloaddition of o-Quinolinone Quinone Methide and Vinyl Thioether [J]. J. Am. Chem. Soc., 2013, 135(13): 4996-4999.

[12] Sun F, Li M, He C, et al. Cleavage of the C(O)-S Bond of Thioesters by Palladium/Norbornene/Copper Cooperative Catalysis): An Efficient Synthesis of 2-(Arylthio)aryl Ketones [J]. J. Am. Chem. Soc., 2016, 138(24): 7456-7459.

[13] Fu Y, Su Y, Xu Q, et al. CuI Promoted Sulfenylation of Organozinc Reagents with Arylsulfonyl Chlorides [J]. RSC Adv., 2017, 7(10): 6018-6022.

[14] Eichman CC, Stambuli JP. Transition Metal Catalyzed Synthesis of Aryl Sulfides [J]. Molecules, 2011, 16(1): 590-608.

[15] Gangjee A, Zeng Y, Talreja T, et al. Design and Synthesis of Classical and Nonclassical 6-Arylthio-2,4-diamino-5-ethylpyrrolo [2,3-d]pyrimidines as Antifolates [J]. J. Med. Chem., 2007, 50(13): 3046-3053.

[16] Liang Y, Wu Y, Feng D, et al. Development of New Semiconducting Polymers for High Performance Solar Cells [J]. J. Am. Chem. Soc., 2008, 131(1): 56-57.

[17] Qiao JX, Lam P. Copper-Promoted Carbon-Heteroatom Bond Cross-Coup ling with Boronic Acids and Derivatives [J]. Synthesis, 2011, 42(6): 829-856.

[18] Cai J, Cai J, Zheng P, et al. Chiral Carbon-sulfur Center Formation Via Pd-catalyzed Asymmetric Allylic Thioetherification): Synthesis of Allylic Thioethers [J]. RSC Adv., 2017, 7(1): 256-259.

[19] Ke F, Qu Y, Jiang Z, et al. An Efficient Copper-Catalyzed Carbon-Sulfur Bond Formation Protocol in Water [J]. Org. Lett., 2011, 13(3): 454-457.

[20] Xu HJ, Zhao YQ, Feng T, et al. Chan-Lam-Type S-Arylation of Thiols with Boronic Acids at Room Temperature [J]. J. Org. Chem., 2012, 77(6): 2878-2884.

[21] Correa A, Carril M, Bolm C. Iron-Catalyzed S-Arylation of Thiols with Aryl Iodides [J]. Angew. Chem. Int. Ed., 2008, 47(15): 2880-2883.

[22] Qiao Z, Jiang X. Recent Developments in Sulfur-carbon Bond Formation Reaction Involving Thiosulfates [J]. Org. Biomol. Chem., 2017, 15(9): 1942-1946.

[23] Qiao Z, Ge N, Jiang X. CO2-promoted Oxidative Cross-coupling Reaction for C-S Bond Formation Via Masked Strategy in an Odourless Way [J]. Chem. Commun., 2015, 51(51): 10295-10298.

[24] Sujatha A, Thomas AM, Thankachan AP, et al. Recent Advances in Copper-catalyzed C-S Cross-coupl ing Reactions [J]. Arkivoc, 2015, 1(1): 1-28.

[25] Panova YS, Kashin AS, Vorobev MG, et al. Nature of the Copper-Oxide- Mediated C-S Cross-Coupling Reaction): Leaching of Catalytically Active Species from the Metal Oxide Surface [J]. ACS Catal., 2016, 6(6): 3637-3643.

[26] Desnoyer AN, Love JA. Recent Advances in Well-defined, Late Transition Metal Complexes That Make and/or Break C-N, C-O and C-S Bonds [J]. Chem. Soc. Rev., 2017, 46(1): 197-238.

[27] Gray VJ, Wilden JD. The Chemistry of Ynol and Thioynol Ethers [J]. Org. Biomol. Chem., 2016, 14(41): 9695-9711.

[28] Bates CG, Gujadhur RK, Venkataraman D. A General Method for the Formation of Aryl-Sulfur Bonds Using Copper(I) Catalysts [J]. Org. Lett., 2002, 4(16): 2803-2806.

[29] Li Y, Pu J, Jiang X. A Highly Efficient Cu-Catalyzed S-Transfer Reaction): From Amine to Sulfide [J]. Org. Lett., 2014, 16(10): 2692-2695.

[30] Jammi S, Barua P, Rout L, et al. Efficient Ligand-free Nickel- catalyzed C-S Cross-coupling of Thiols with Aryl Iodides [J]. Tetrahedron Lett., 2008, 49(9): 1484-1487.

[31] Cai M, Wang Y, Hao W. Palladium-catalyzed Addition of Diaryl Disulfides and Diselenides to Terminal Alkynes in Room Temperature Ionic Liquids [J]. Green Chem., 2007, 9(11): 1180-1184.