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New reagents of containing fluorine and sulfur-containing in organic reactions

  • WANG Naixing
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  • Technical Institute of Physics and Chemistry CAS, Beijing 100190, China

Received date: 2023-11-22

  Revised date: 2024-09-10

  Online published: 2025-01-06

Abstract

The research and development of new reagents are of great significance for organic synthesis. In recent years, some new reagents with universal applicability have been constantly emerging. This article introduces the latest research progress on new reagents for difluoromethylation and trifluoromethylation. Introduced some new sulfur-containing reagents. New reagents DMSO-I2 and DMSO-TsCl for sulfur methylation were introduced detailedly, The sulfur-containing reagent Na2S2O4-TBHP (TBHP, t-butylhydroperoxide) is a new reagent used for selective oxidation of aromatic alcohols to aldehydes which was also known as Wang's reagent.

Cite this article

WANG Naixing . New reagents of containing fluorine and sulfur-containing in organic reactions[J]. Science & Technology Review, 2024 , 42(23) : 98 -107 . DOI: 10.3981/j.issn.1000-7857.2023.11.01761

References

[1] Ghari H, Li Y F, Roohzadeh R, et al. Gold-catalyzed domino cyclization-alkynylation reactions with EBX reagents: New insights into the reaction mechanism[J]. Dalton Transactions, 2017, 46(36): 12257-12262.
[2] Blahun O P, Redka M O, Voitenko Z V, et al. 2, 2-difluorovinyl pinacolborane-A new versatile reagent for the suzuki-miyaura reaction[J]. European Journal of Organic Chemistry, 2019(37): 6417-6421.
[3] Piazza C, Millot N, Knochel P. New preparation of benzylic zinc reagents via a fragmentation reaction[J]. Journal of Organometallic Chemistry, 2001, 624(1/2): 88-95.
[4] Ando K, Kobayashi T, Uchida N. Practical methylenation reaction for aldehydes and ketones using new Julia-type reagents[J]. Organic Letters, 2015, 17(10): 2554-2557.
[5] Carrera N, Gutiérrez E, Benavente R, et al. Stannylated polynorbornenes as new reagents for a clean Stille reaction [J]. Chemistry-A European Journal, 2008, 14(32): 10141- 10148.
[6] Fujiwara Y, Dixon J A, Rodriguez R A, et al. A new reagent for direct difluoromethylation[J]. Journal of the American Chemical Society, 2012, 134(3): 1494-1497.
[7] Surya Prakash G K, Weber C, Chacko S, et al. New electrophilic difluoromethylating reagent[J]. Organic Letters, 2007, 9(10): 1863-1866.
[8] Tung T T, Christensen S B, Nielsen J. Difluoroacetic acid as a new reagent for direct C-H difluoromethylation of heteroaromatic compounds[J]. Chemistry-A European Journal, 2017, 23(72): 18125-18128.
[9] Yuan W J, Tong C L, Xu X H, et al. Copper-mediated oxidative chloro- and bromodifluoromethylation of phenols [J]. Journal of the American Chemical Society, 2023, 145(44): 23899-23904.
[10] Liu H, He X, Chen Z C, et al. N-trifluoromethyl succinimide as a new reagent for direct C-H trifluoromethylation of free anilines[J]. Chemistry-An Asian Journal, 2023, 18(8): e202300039.
[11] Sato A, Han J L, Ono T, et al. Introducing a new radical trifluoromethylation reagent[J]. Chemical Communications, 2015, 51(27): 5967-5970.
[12] Guo S, Cong F, Guo R, et al. Asymmetric silver-catalysed intermolecular bromotrifluoromethoxylation of alkenes with a new trifluoromethoxylation reagent[J]. Nature Chemistry, 2017, 9(6): 546-551.
[13] Zhao G, Wu H, Xiao Z, et al. Trifluoromethylation of haloarenes with a new trifluoro-methylating reagent Cu (O2CCF2SO2F)2[J]. RSC Advances, 2016, 6: 50250- 50254.
[14] Liu P, Liu W B, Li C J. Catalyst-free and redox-neutral innate trifluoromethylation and alkylation of aromatics enabled by light[J]. Journal of the American Chemical Society, 2017, 139(40): 14315-14321.
[15] Kalim J, Duhail T, Le T N, et al. Merging hypervalent iodine and sulfoximine chemistry: A new electrophilic trifluoromethylation reagent[J]. Chemical Science, 2019, 10(45): 10516-10523.
[16] Yang Y, Tang R H, Abid S, et al. Organophotocatalyzed synthesis of vinyl-SCF3 and benzoyl-SCF3 using a new N-(SCF3)(CF3)-shelf-stable reagent[J]. European Journal of Organic Chemistry, 2023, 26(36): e202300619.
[17] Castillo-Pazos D J, Lasso J D, Li C J. Synthesis of α- (perfluoroalkylsulfonyl)propiophenones: A new set of reagents for the light-mediated perfluoroalkylation of aromatics[J]. Beilstein Journal of Organic Chemistry, 2022, 18: 788-795.
[18] Zhou M, Ni C, Zeng Y, et al. Trifluoromethyl benzoate: A versatile trifluoromethoxylation reagent[J]. Journal of the American Chemical Society, 2018, 140: 6801.
[19] Wu Y H, Wang N X, Zhang T, et al. Iodine-mediated synthesis of methylthio-substituted catechols from cyclohexanones[J]. Advanced Synthesis & Catalysis, 2019, 361(12): 3008-3013.
[20] Zhang L Y, Wu Y H, Wang N X, et al. Methylthiolation for electron-rich heteroarenes with DMSO-TsCl[J]. European Journal of Organic Chemistry, 2021(9): 1446-1451.
[21] Bai C B, Wang N X, Lan X W, et al. An unexpected controlled new oxidant: SO 4(·- ) [J]. Scientific Reports, 2016, 6: 20163.
[22] Bai C B, Wang N X, Wang Y J, et al. A petal-type chiral NADH model: Design, synthesis and its asymmetric reduction[J]. Scientific Reports, 2015, 5: 17458.
[23] Bai C B, Wang N X, Wang Y J, et al. A new oxidation system for the oxidation of Hantzsch-1, 4-dihydropyridines and polyhydroquinoline derivatives under mild conditions[J]. RSC Advances, 2015, 5(122): 100531- 100534.
[24] Corey E J, Suggs J W. Pyridinium chlorochromate. An efficient reagent for oxidation of primary and secondary alcohols to carbonyl compounds[J]. Tetrahedron Letters, 1975, 16(31): 2647-2650.
[25] Taylor R J K, Reid M, Foot J, et al. Tandem oxidation processes using manganese dioxide: Discovery, applications, and current studies[J]. Accounts of Chemical Research, 2005, 38(11): 851-869.
[26] Hoover J M, Ryland B L, Stahl S S. Mechanism of copper(I)/TEMPO-catalyzed aerobic alcohol oxidation[J]. Journal of the American Chemical Society, 2013, 135(6): 2357-2367.
[27] Ghosh P P, Mukherjee P, Das A R. Triton-X-100 catalyzed synthesis of 1, 4-dihydropyridines and their aromatization to pyridines and a new one pot synthesis of pyridines using visible light in aqueous media[J]. RSC Advances, 2013, 3(22): 8220-8226.
[28] Chen D D, Wang N X, Lan X W, et al. Efficient synthesis of polysubstituted tetrahydrothiopyran sulfoxides by the reaction of α, β -unsaturated ketones and Na2S[J]. Current Organic Synthesis, 2016, 13(4): 651-655.
[29] Gao W C, Liu J R, Jiang X F. Phthalimide-based-SSCF 3 reagent for enantioselective dithiotrifluoromethylation [J]. Organic Chemistry Frontiers, 2021, 8(6): 1275-1279.
[30] Zhang J X, Wang Y J, Zhang W, et al. Selective nickeland manganese-catalyzed decarboxylative cross coupling of some α, β -unsaturated carboxylic acids with cyclic ethers[J]. Scientific Reports, 2014, 4: 7446-7451.
[31] Zhang W, Wang N X, Bai C B, et al. Manganese-mediated coupling reaction of vinylarenes and aliphatic alcohols[J]. Scientific Reports, 2015, 5: 15250.
[32] Lan X W, Wang N X, Zhang W, et al. Copper/manganese cocatalyzed oxidative coupling of vinylarenes with ketones[J]. Organic Letters, 2015, 17(18): 4460-4463.
[33] Lan X W, Wang N X, Bai C B, et al. Unactivated C (sp3) -H bond functionalization of alkyl nitriles with vinylarenes and mechanistic studies[J]. Organic Letters, 2016, 18(23): 5986-5989.
[34] Zhang T, Lan X W, Zhou Y Q, et al. C(sp3) -H bond functionalization of non-cyclic ethers by decarboxylative oxidative coupling with α, β-unsaturated carboxylic acids[J]. Science China Chemistry, 2018, 61(2): 180-183.
[35] Yan Z, Wang N X, Gao X W, et al. A copper (II) acetate mediated oxidative-coupling of styrenes and ethers through an unactivated C(sp3) -H bond functionalization [J]. Advanced Synthesis & Catalysis, 2019, 361(5): 1007-1011.
[36] Yan Z, Wang N X, Zhang L Y, et al. The C(sp3)-H bond functionalization of thioethers with styrenes with insight into the mechanism[J]. Organic & Biomolecular Chemistry, 2022, 20(29): 5845-5851.
[37] Zhang T, Wu Y H, Wang N X, et al. Advances in C (sp3) -H bond functionalization via radical processes[J]. Synthesis, 2019, 51(24): 4531-4548.
[38] Wang N X, Zhang L Y, Wu Y H, et al. C(sp3)-H bond functionalization of alcohols, ketones, nitriles, ethers and amides using TBHP as a radical initiator[J]. Synlett, 2021, 32(1): 23-29.
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