Successful trifluoromethoxy-containing pharmaceuticals and agrochemicals (2024)

1. Jiang Liu
2. Weikang Lin
3. Alexander E. Sorochinsky
4. Greg Butler
5. Aitor Landa
6. Jianlin Han
7. Vadim A. Soloshonok

1. Banks, Direct fluorination of bis(trifluoromethanesulfonyl)imide and its lithium salt and related studies, J. Fluorine Chem., № 122, с. 271
   https://doi.org/10.1016/S0022-1139(01)00510-3
2. Yang, Advances in catalytic enantioselective fluorination, mono-, di-, and trifluoro-methylation, and trifluoromethylthiolation reactions, Chem. Rev., № 115, с. 826
   https://doi.org/10.1021/cr500277b
3. Syvret, Novel process for generating useful electrophiles from common anions using Selectfluor fluorination agent, J. Org. Chem., № 67, с. 4487
   https://doi.org/10.1021/jo020053u
4. Bravo, Chiral sulfoxide controlled asymmetric additions to C,N double bond. An efficient approach to stereochemically defined α-fluoroalkyl amino compounds, Tetrahedron, № 54, с. 12789
   https://doi.org/10.1016/S0040-4020(98)00779-0
5. Xu, Synthetic methods for compounds having CF3–S units on carbon by trifluoromethylation, trifluoromethylthiolation, triflylation, and related reactions, Chem. Rev., № 115, с. 731
   https://doi.org/10.1021/cr500193b
6. Ohkura, Chemo- and regioselectivity in the reactions between highly electrophilic fluorine containing dicarbonyl compounds and amines. improved synthesis of the corresponding imines/enamines, Tetrahedron, № 59, с. 1647
   https://doi.org/10.1016/S0040-4020(03)00138-8
7. Gondo, Reaction of iodonium ylides of 1, 3-dicarbonyl compounds with HF reagents, Molecules, № 17, с. 6625
   https://doi.org/10.3390/molecules17066625
8. Han, Biomimetic transamination – a metal-free alternative to the reductive amination. Application for generalized preparation of fluorine-containing amines and amino acids, Curr. Org. Synth., № 8, с. 281
   https://doi.org/10.2174/157017911794697277
9. Syvret, Selective fluorination of an aryltriazolinone herbicide intermediate, J. Fluorine Chem., № 125, с. 33
   https://doi.org/10.1016/j.jfluchem.2003.09.002
10. Röschenthaler, Asymmetric synthesis of phosphonotrifluoroalanine and its derivatives using N-tert-butanesulfinyl imine derived from fluoral, Tetrahedron Lett., № 53, с. 539
    https://doi.org/10.1016/j.tetlet.2011.11.096
11. Wiehn, Electrophilic trifluoromethylation of arenes and N-heteroarenes using hyperva-lent iodine reagents, J. Fluorine Chem., № 131, с. 951
    https://doi.org/10.1016/j.jfluchem.2010.06.020
12. Turcheniuk, Efficient asymmetric synthesis of trifluoromethylated β-aminophosphonates and their incorporation into dipeptides, Chem. Commun., № 48, с. 11519
    https://doi.org/10.1039/c2cc36702e
13. Merino, Addition of CF3 across unsaturated moieties: a powerful functionalization tool, Chem. Soc. Rev., № 43, с. 6598
    https://doi.org/10.1039/C4CS00025K
14. Ma, Strategies for nucleophilic, electrophilic, and radical trifluoromethylations, J. Fluorine Chem., № 128, с. 975
    https://doi.org/10.1016/j.jfluchem.2007.04.026
15. Yamada, Efficient asymmetric synthesis of novel 4-substituted and configurationally stable analogs of thalidomide, Org. Lett., № 8, с. 5625
    https://doi.org/10.1021/ol0623668
16. Wang, Fluorine in pharmaceutical industry: fluorine-containing drugs introduced to the market in the last decade (2001–2011), Chem. Rev., № 114, с. 2432
    https://doi.org/10.1021/cr4002879
17. Zhou, Next generation of fluorine-containing pharmaceuticals, compounds currently in phase II–III clinical trials of major pharmaceutical companies: new structural trends and therapeutic areas, Chem. Rev., № 116, с. 422
    https://doi.org/10.1021/acs.chemrev.5b00392
18. Zhu, Modern approaches for asymmetric construction of carbon–fluorine quaternary stereogenic centers: synthetic challenges and pharmaceutical needs, Chem. Rev., № 118, с. 3887
    https://doi.org/10.1021/acs.chemrev.7b00778
19. Han, Chemical aspects of human and environmental overload with fluorine, Chem. Rev., № 121, с. 4678
    https://doi.org/10.1021/acs.chemrev.0c01263
20. Mei, Applications of fluorine-containing amino acids for drug design, Eur. J. Med. Chem., № 186
    https://doi.org/10.1016/j.ejmech.2019.111826
21. Mei, Tailor-made amino acids and fluorinated motifs as prominent traits in the modern pharmaceuticals, Chem. Eur. J., № 26, с. 11349
    https://doi.org/10.1002/chem.202000617
22. Mei, Fluorine-containing drugs approved by the FDA in 2018, Chem. Eur. J., № 25, с. 11797
    https://doi.org/10.1002/chem.201901840
23. Mei, Fluorine-containing drugs ap-proved by the FDA in 2019, Chin. Chem. Lett., № 31, с. 2401
    https://doi.org/10.1016/j.cclet.2020.03.050
24. Yu, Fluorine-containing pharmaceuticals approved by the FDA in 2020: synthesis and biological activity, Chin. Chem. Lett., № 32, с. 3342
    https://doi.org/10.1016/j.cclet.2021.05.042
25. Han, Next generation orga-nofluorine containing blockbuster drugs, J. Fluorine Chem., № 239
    https://doi.org/10.1016/j.jfluchem.2020.109639
26. Turcheniuk, Recent advances in the synthesis of fluorinated aminophosphonates and aminophosphonic acids, RSC Adv., № 3, с. 6693
    https://doi.org/10.1039/c3ra22891f
27. Fujiwara, Successful fluorine-containing herbicide agrochemicals, J. Fluorine Chem., № 167, с. 16
    https://doi.org/10.1016/j.jfluchem.2014.06.014
28. Isanbor, Fluorine in medicinal chemistry: a review of anti-cancer agents, J. Fluorine Chem., № 127, с. 303
    https://doi.org/10.1016/j.jfluchem.2006.01.011
29. Xu, Truxene-BODIPY dyads and triads: synthesis, spectroscopic characterization, one and two-photon absorption properties and electrochemistry, Dye. Pigment., № 179
    https://doi.org/10.1016/j.dyepig.2020.108380
30. Alonso, Carbon trifluoromethylation reactions of hydrocarbon derivatives and heteroarenes, Chem. Rev., № 115, с. 1847
    https://doi.org/10.1021/cr500368h
31. Campbell, Modern carbon–fluorine bond forming reactions for aryl fluoride synthesis, Chem. Rev., № 115, с. 612
    https://doi.org/10.1021/cr500366b
32. Zhu, Recent advances in the trifluoromethyl-ation methodology and new CF3-containing drugs, J. Fluorine Chem., № 167, с. 37
    https://doi.org/10.1016/j.jfluchem.2014.06.026
33. Liu, Trifluoromethyltrimethylsilane: nucleophilic trifluoromethylation and beyond, Chem. Rev., № 115, с. 683
    https://doi.org/10.1021/cr400473a
34. Fu, Recent advances on the halo- and cyano-trifluoromethylation of alkenes and alkynes, Molecules, № 26, с. 7221
    https://doi.org/10.3390/molecules26237221
35. Besset, Recent progress in direct introduction of fluorinated groups on alkenes and alkynes by means of C-H bond functionalization, Chem. Eur. J., № 20, с. 16830
    https://doi.org/10.1002/chem.201404537
36. Belhomme, Recent progress toward the introduction of functionalized difluo-romethylated building blocks onto C(sp2) and C(sp) centers, Chem. Eur. J., № 21, с. 12836
    https://doi.org/10.1002/chem.201501475
37. Bravo, Stereoselective additions of α-lithiated alkyl p-tolylsulfoxides to N-PMP fluoroalkyl aldimines. An efficient approach to enantiomerically pure fluoro-amino compounds, J. Org. Chem., № 62, с. 3424
    https://doi.org/10.1021/jo970004v
38. Ni, Advances in transition-metal-mediated di-and monofluoroalkylations, Acta Chim. Sin., № 73, с. 90
    https://doi.org/10.6023/A14110758
39. Pan, Progress in fluoroalkylation of multicomponent, Chin. J. Org. Chem., № 41, с. 983
    https://doi.org/10.6023/cjoc202007025
40. Han, Electrophilic fluorination using HF as a source of fluorine, Molecules, № 25, с. 2116
    https://doi.org/10.3390/molecules25092116
41. Qiu, Advances in Trifluoromethylation-promoted functional group migration of alkenes, Chin. J. Org. Chem., № 41, с. 1821
    https://doi.org/10.6023/cjoc202009036
42. Li, Recent advance in asymmetric trifluoromethylthiolation, Acta Chim. Sin., № 76, с. 913
    https://doi.org/10.6023/A18070306
43. Landelle, Recent advances in transition metal-catalyzed Csp2-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation, Beilstein J. Org. Chem., № 9, с. 2476
    https://doi.org/10.3762/bjoc.9.287
44. Landelle, Trifluoromethyl ethers and–thioethers as tools for medicinal chemistry and drug discovery, Curr. Top. Med. Chem., № 14, с. 941
    https://doi.org/10.2174/1568026614666140202210016
45. Soloshonok, Gold(I)-catalyzed asymmetric aldol reaction of fluorinated benzaldehydes with α-isocyanoacetamide, Tetrahedron Asymmetry, № 5, с. 1091
    https://doi.org/10.1016/0957-4166(94)80059-6
46. Manteau, New trends in the chemistry of α-fluorinated ethers, thioethers, amines and phosphines, J. Fluorine Chem., № 131, с. 140
    https://doi.org/10.1016/j.jfluchem.2009.09.009
47. Leroux, Trifluoromethyl ethers–synthesis and properties of an unusual substituent, Beilstein J. Org. Chem., № 4, с. 13
    https://doi.org/10.3762/bjoc.4.13
48. Wang, Advances in the development of trifluoro-methoxylation reagents, Symmetry, № 13, с. 2380
    https://doi.org/10.3390/sym13122380
49. Inoue, Contribution of organofluorine compounds to pharmaceuticals, ACS Omega, № 5, с. 10633
    https://doi.org/10.1021/acsomega.0c00830
50. Bryson, Riluzole: a review of its pharmacodynamic and pharmaco*kinetic properties and ther-apeutic potential in amyotrophic lateral sclerosis, Drugs, № 52, с. 549
    https://doi.org/10.2165/00003495-199652040-00010
51. Anzini, Synthesis and biological evaluation of amidine, guanidine, and thiourea derivatives of 2-amino-(6-trifluoromethoxy)benzothiazole as neuroprotective agents potentially useful in brain diseases, J. Med. Chem., № 53, с. 734
    https://doi.org/10.1021/jm901375r
52. Mancini, Synthesis and biological evaluation of a new class of benzothia-zines as neuroprotective agents, Eur. J. Med. Chem., № 126, с. 614
    https://doi.org/10.1016/j.ejmech.2016.11.053
53. Jimonet, Riluzole series. Synthesis and in vivo “antiglutamate” activity of 6-substituted-2-benzothiazolamines and 3-substituted-2-imino-benzothiazolines, J. Med. Chem., № 42, с. 2828
    https://doi.org/10.1021/jm980202u
54. Jordan, Efficient conversion of substituted aryl thioureas to 2-aminobenzothiazoles using ben-zyltrimethylammonium tribromide, J. Org. Chem., № 68, с. 8693
    https://doi.org/10.1021/jo0349431
55. b)J. Mizoule, Medicament based on 2-amino-6-trifluoromethoxy-benzothiazole. (1983) US4370338.
56. c)C.S.R. Kokatam, A.N. Chimmiri, P. Kumar, G.A. Raman, K. Masthanraj, R.T. Srinivasan, K. Kumar, R. Anand, Process for the preparation of 4-substituted-1-(trifluoromethoxy)benzene compounds. (2014) WO2016125185 A2.
57. Ryan, Delamanid: first global approval, Drugs, № 74, с. 1041
    https://doi.org/10.1007/s40265-014-0241-5
58. Sasaki, Synthesis and antituberculosis activity of a novel series of optically active 6-nitro-2,3-dihydroimidazo[2,1-b]oxazoles, J. Med. Chem., № 49, с. 7854
    https://doi.org/10.1021/jm060957y
59. Patterson, The anti-tubercular drug delamanid as a potential oral treatment for visceral leishmaniasis, Elife, № 5, с. e09744
    https://doi.org/10.7554/eLife.09744
60. b)T. Wang, T. Xin, H. Fan, Y. Chen, (6,7-dihydro-2-nitro-5H-imidazol[2,1-b][1,3]oxazin-6-yl) amide compounds, preparation methods and uses thereof. (2013) US 20130143864 A1.
61. Sasaki, Synthesis and antituberculosis activity of a novel series of optically active 6-nitro-2,3-dihydroimidazo[2,1-b]oxazoles, J. Med. Chem., № 49, с. 7854
    https://doi.org/10.1021/jm060957y
62. Casey, FDA approval summary: sonidegib for locally advanced basal cell carcinoma, Clin. Cancer Res., № 23, с. 2377
    https://doi.org/10.1158/1078-0432.CCR-16-2051
63. Pan, Discovery of NVP-LDE225, a potent and selective smoothened antagonist, ACS Med. Chem. Lett., № 1, с. 130
    https://doi.org/10.1021/ml1000307
64. Burness, Sonidegib: first global approval, Drugs, № 75, с. 1559
    https://doi.org/10.1007/s40265-015-0458-y
65. Takale, An environmentally responsible 3-pot, 5-step synthesis of the anti-tumor agent sonidegib using ppm levels of Pd catalysis in water, Green Chem., № 21, с. 6258
    https://doi.org/10.1039/C9GC03495A
66. b)F. Yang, P.C. Tang, Q. Dong, W. Tu, J. Fan, D. Guan, G. Shen, Y. Wang, J. Yuan, L. Zhang, C-aryl glucoside derivatives, preparation process and pharmaceutical use thereof. (2013) US 2013130997 A1.
67. c)A.E. Bailey, D.R. Hill, C.N.W. Hsiao, R. Kurukulasuriya, S. Wittenberger, T. McDermott, M.A. McLaughlin, Process for the preparation of matrix metalloproteinase inhibitors. (2002) US2002019539 A1.
68. Thompson, Development of (6R)2-Nitro-6-[4-(trifluoromethoxy)phenoxy]-6,7-dihydro5Himidazo[2,1b][1,3]oxazine (DNDI-8219): a new lead for visceral Leishmaniasis, J. Med. Chem., № 61, с. 2329
    https://doi.org/10.1021/acs.jmedchem.7b01581
69. Keam, Pretomanid: first approval, Drugs, № 79, с. 1797
    https://doi.org/10.1007/s40265-019-01207-9
70. Baptista, Untargeted metabolomics reveals a new mode of action of pretomanid (PA-824), Sci. Rep., № 8, с. 5084
    https://doi.org/10.1038/s41598-018-23110-1
71. Rakesh, Synthesis and evaluation of pretomanid (PA-824) oxazolidinone hybrids, Bioorg. Med. Chem. Lett., № 26, с. 388
    https://doi.org/10.1016/j.bmcl.2015.12.002
72. Orita, Integration of solventless reaction in a multi-step process: application to an efficient synthesis of PA-824, Adv. Synth. Catal., № 349, с. 2136
    https://doi.org/10.1002/adsc.200700119
73. b)A. Marhold, P. Muller, Process for preparing 2-(4-trifluoromethoxyphenyl)ethylamide and 4-bromomethyl- and 4-chloromethyl-1-trifluoromethoxylbenzene. (2002) US2002082454 A1.
74. Weston, Recent progress in potassium channel opener pharmacology, Biochem. Pharmacol., № 43, с. 47
    https://doi.org/10.1016/0006-2952(92)90659-7
75. Sanfilippo, Thiophene systems. 14. synthesis and antihypertensive activity of novel 7-(Cyclic ami-do)-6-hydroxythieno[3,2-h]pyrans and related compounds as new potassium channel activators, J. Med. Chem., № 35, с. 4425
    https://doi.org/10.1021/jm00101a020
76. Soll, Antihypertensive benzopyran-related potassium channel activators: a role for lipophilicity, Bioorg. Med. Chem. Lett., № 1, с. 591
    https://doi.org/10.1016/S0960-894X(01)81157-4
77. Quagliato, The synthesis and structural characterization of way-120,491; a novel potassium channel activator, Bioorg. Med. Chem. Lett., № 1, с. 39
    https://doi.org/10.1016/S0960-894X(01)81086-6
78. Ishaaya, Novaluron (Rimon), a Novel IGR: potency and cross-resistance, Arch. Insect Biochem., № 54, с. 157
    https://doi.org/10.1002/arch.10113
79. Arredondo-Jiménez, Effect of Novaluron (Rimon® 10 EC) on the mosquitoes Anopheles albi-manus, Anopheles pseudopunctipennis, Aedes aegypti, Aedes albopictus and Culex quinquefasciatus from Chiapas, Mexico, Med. Vet. Entomol., № 20, с. 377
    https://doi.org/10.1111/j.1365-2915.2006.00656.x
80. Elek, Novaluron nanoparticles: formation and potential use in controlling agricultural insect pests, Colloids Surf. A Physicochem. Eng. Asp., № 372, с. 66
    https://doi.org/10.1016/j.colsurfa.2010.09.034
81. P. Massardo, F. Rama, P. Piccardi, V. Caprioll, N-(2,6-difluorobenzoyl)-N’-3-chloro-4-[1,1,2-trifluoromethoxy] ethoxy] phenyl urea having insecticidal activity. (1988) EP0271923A1.
82. Y. Ma, G. Yang, H. Yang, P. Wei, C. Zeng, K. Liu, H. Chai, M. Wang, Perfluoromethyl vinyl ether preparation method. (2016) CN105367392.
83. Wang, Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation, Chin. Chem. Lett.
84. Tan, A novel quinolone insecticide and acaricide flometoquin and its development, Mod. Agrochem., № 18, с. 45
85. C.S.R. Kokatam, A.N. Chimmiri, P. Kumar, G.A. Raman, K. Masthanraju, R.T. Srinivasan, K. Kumar, R. Anand, Process for the preparation of 4-substituted-1-(trifluoromethoxy)benzene compounds. (2016) WO2016125185A2.
86. Y. Kato, S. Shimano A. Morikawa, H. Hotta, K. Yamamoto, N. Nakanishi, N. Minowa, H. Kurihara, Method for produc-ing 6-aryloxyquinoline derivative and intermediate thereof. (2009) EP2305649A1.
87. K.H. Müller, J. Kluth, K. Lürssen, H.J. Santel, R.R. Schmidt, Herbicidal sulphonylaminocarbonyl triazolinones having substituents bonded via oxygen. (1996) US005534486A.
88. Eliason, Phytotoxicity and persistence of flucarbazone-sodium in soil, Weed Sci., № 52, с. 857
    https://doi.org/10.1614/WS-03-047R2
89. J.T. Brisow, New crystal form of flucarbazone-sodium. (2021) WO2021134242 A1.
90. W. Jing, Z. Yan, C. Bu, X. Hu, Flucarbazone-sodium synthesis method. (2017) CN106478533A.
91. a)A. Schnatterer, M. Hermann, Process for the preparation of aromatic or heteroaromatic sulphonyl chlorides. (2002) US6365780 B1.
92. Patil, Design and synthesis of triazolopyrimidine acylsulfonamides as novel anti-mycobacterial leads acting through inhibition of acetohydroxyacid synthase, Bioorg. Med. Chem. Lett., № 24, с. 2222
    https://doi.org/10.1016/j.bmcl.2014.02.054
93. Yang, Toxic effects of thifluzamide on zebrafish (Danio rerio), J. Hazard. Mater., № 307, с. 127
    https://doi.org/10.1016/j.jhazmat.2015.12.055
94. Yao, Toxicity of thifluzamide in earthworm (Eisenia fetida), Ecotoxicol. Environ. Saf., № 188
    https://doi.org/10.1016/j.ecoenv.2019.109880
95. Cao, Residual levels and dietary risk assessment of thifluzamide in peanut, Int. J. Environ. Anal. Chem.
96. G.H. Alt, J.K. Pratt, W.G. Phillips, G.H. Srouji, Substituted thiazoles and their use as fungicides. (1989) EP0371950A2.
97. Neware, Flurprimidol: a growth retardant, J. Pharmacogn. Phytochem., № 8, с. 141
98. Krug, Flurprimidol is effective at controlling height of star gazer' oriental lily, Horttechnology, № 15, с. 373
    https://doi.org/10.21273/HORTTECH.15.2.0373
99. Stier, Flurprimidol effects on Kentucky bluegrass under reduced irradiance, Crop Sci., № 39, с. 1423
    https://doi.org/10.2135/cropsci1999.3951423x
100. R.L. Benefiel, E.V. Krumkalns, Fluoroalkoxyphenyl-substituted nitrogen heterocycles as plant stunting agents. (1976) US3967949A.
101. Yagupolskii, Sintez proizvodnykh feniltriftormetilovogo efira, Dokl. Akad. Nauk. SSSR, № 105, с. 100
102. Besset, New entries toward the synthesis of OCF3-containing molecules, Org. Chem. Front., № 3, с. 1004
     https://doi.org/10.1039/C6QO00164E
103. Mathey, Reaction de MoF6 avec chlorothioformiates d'aryle nouvelle synthese des aryl trifluoromethyleth-ers ArOCF3, Tetrahedron Lett., № 25, с. 2253
     https://doi.org/10.1016/S0040-4039(01)87608-5
104. Feiring, Chemistry in hydrogen fluoride. 7. A novel synthesis of aryl trifluoromethyl ethers, J. Org. Chem., № 44, с. 2907
     https://doi.org/10.1021/jo01330a017
105. Kuroboshi, Oxidative desulfurization-fluorination of xanthates. A convenient synthesis of tri-fluoromethyl ethers and difluoro (methylthio) methyl ethers, Tetrahedron Lett., № 33, с. 4173
     https://doi.org/10.1016/S0040-4039(00)74681-8
106. Kanie, A convenient synthesis of trifluoromethyl ethers by oxidative desulfurization-fluorination of dithiocarbonates, Bull. Chem. Soc. Jpn., № 73, с. 471
     https://doi.org/10.1246/bcsj.73.471
107. Kuroboshi, Oxidative desulfurization-fluorination: a facile entry to a wide variety of orga-nofluorine compounds leading to novel liquid-crystalline materials, Adv. Synth. Catal., № 343, с. 235
     https://doi.org/10.1002/1615-4169(20010330)343:3<235::AID-ADSC235>3.0.CO;2-0
108. Shimizu, Modern synthetic methods for fluorine-substituted target molecules, Angew. Chem. Int. Ed., № 44, с. 214
     https://doi.org/10.1002/anie.200460441
109. Umemoto, CF3 oxonium salts, O-(Trifluoromethyl)dibenzofuranium salts: in situ synthesis, properties, and application as a real CF3+ species reagent, J. Org. Chem., № 72, с. 6905
     https://doi.org/10.1021/jo070896r
110. Koller, Zinc-mediated formation of trifluoromethyl ethers from alcohols and hypervalent iodine trifluoromethylation reagents, Angew. Chem. Int. Ed., № 48, с. 4332
     https://doi.org/10.1002/anie.200900974
111. Stanek, Reactivity of a 10-I-3 hypervalent iodine trifluoromethylation reagent with phenols, J. Org. Chem., № 73, с. 7678
     https://doi.org/10.1021/jo8014825
112. Sorochinsky, Optical purifications via self-disproportionation of enantiomers by achiral chromatography; case study of a series of α-CF3-containing secondary alcohols, Chirality, № 25, с. 365
     https://doi.org/10.1002/chir.22180
113. Han, Self-disproportionation of enantiomers via sublimation; new and truly green dimension in optical purification, Curr. Org. Synth., № 8, с. 310
     https://doi.org/10.2174/157017911794697303
114. Sorochinsky, Self-disproportionation of enantiomers of chiral, non-racemic fluoroorganic compounds: role of fluorine as enabling element, Synthesis, № 45, с. 141
115. Ueki, Rational application of self-disproportionation of enantiomers via sublimation—a novel methodological dimension for enantiomeric purifications, Tetrahedron Asymmetry, № 21, с. 1396
     https://doi.org/10.1016/j.tetasy.2010.04.040
116. Soloshonok, Self-disproportionation of enantiomers on achiral phase chromatography. One more example of fluorine's magic powers, Chim. Oggi Chem. Today, № 24, с. 44
117. Han, The self-disproportionation of enantiomers (SDE): a men-ace or an opportunity?, Chem. Sci., № 9, с. 1718
     https://doi.org/10.1039/C7SC05138G
118. Soloshonok, A question of policy: should tests for the self-disproportionation of enantiomers (SDE) be mandatory for reports involving scalemates?, Tetrahedron Asymmetry, № 28, с. 1430
     https://doi.org/10.1016/j.tetasy.2017.08.020
119. Han, Chiral sulfoxides: advances in asymmetric synthesis and problems with the accurate determination of the stereochemical outcome, Chem. Soc. Rev., № 47, с. 1307
     https://doi.org/10.1039/C6CS00703A
120. Han, Recommended tests for the self-disproportionation of enantiomers (SDE) to ensure accurate reporting of the stereochemical outcome of enantioselective reactions, Molecules, № 26, с. 2757
     https://doi.org/10.3390/molecules26092757
121. Han, A call for a change in policy regarding the necessity for SDE tests to validate the veracity of the outcome of enantioselective syntheses, the inherent chiral state of natural products, and other cases involving enantioenriched samples, Molecules, № 26, с. 3994
     https://doi.org/10.3390/molecules26133994

Borylation of Alkenyl Carbamates by Means of Sodium Metal

Hideki Yorimitsu, Shunsuke Koyama, Fumiya Takahashi, Hayate Saito

https://doi.org/10.1055/a-1970-4584 ·

Microwave-assisted Synthesis of Fluorinated Heterocycles

Ram Singh, Chandra Prakash

https://doi.org/10.2174/2213346110666221223140653

About this publication