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Development of N-F fluorinating agents and their fluorinations: Historical perspective
- Teruo Umemoto,
- Yuhao Yang and
- Gerald B. Hammond
Beilstein J. Org. Chem. 2021, 17, 1752–1813, doi:10.3762/bjoc.17.123
- and reactions of these reagents are described chronologically and the review also discusses the relative fluorination power of each reagent and their mechanisms chronicling developments from a historical perspective. Keywords: N-F fluorinating agent; fluorination; fluorodiazoniabicyclo[2.2.2]octane
- salt; fluoropyridinium salt; fluorosulfonimide; Introduction Fluorinated organic compounds occupy an important position in pharmaceuticals [1], agrochemicals [2], and materials [3]. Especially, in the first two areas, the presence of fluorine has attracted attention during the last decades. Nowadays
Graphical Abstract
Scheme 1: Fluorination with N-F amine 1-1.
Scheme 2: Preparation of N-F amine 1-1.
Scheme 3: Reactions of N-F amine 1-1.
Scheme 4: Synthesis of N-F perfluoroimides 2-1 and 2-2.
Scheme 5: Synthesis of 1-fluoro-2-pyridone (3-1).
Scheme 6: Fluorination with 1-fluoro-2-pyridone (3-1).
Figure 1: Synthesis of N-F sulfonamides 4-1a–g.
Scheme 7: Fluorination with N-F reagent 4-1b,c,f.
Scheme 8: Fluorination of alkenyllithiums with N-F 4-1h.
Scheme 9: Synthesis of N-fluoropyridinium triflate (5-4a).
Scheme 10: Synthetic methods for N-F-pyridinium salts.
Figure 2: Synthesis of various N-fluoropyridinium salts. Note: athis yield was the one by the improved method...
Scheme 11: Fluorination power order of N-fluoropyridinium salts.
Scheme 12: Fluorinations with N-F salts 5-4.
Scheme 13: Fluorination of Corey lactone 5-7 with N-F-bis(methoxymethyl) salt 5-4l.
Scheme 14: Fluorination with NFPy.
Scheme 15: Synthesis of the N-F reagent, N-fluoroquinuclidinium fluoride (6-1).
Scheme 16: Fluorinations achieved with N-F fluoride 6-1.
Scheme 17: Synthesis of N-F imides 7-1a–g.
Scheme 18: Fluorination with (CF3SO2)2NF, 7-1a.
Scheme 19: Fluorination reactions of various substrates with 7-1a.
Scheme 20: Synthesis of N-F triflate 8-1.
Scheme 21: Synthesis of chiral N-fluoro sultams 9-1 and 9-2.
Scheme 22: Fluorination with chiral N-fluoro sultams 9-1 and 9-2.
Scheme 23: Synthesis of saccharin-derived N-fluorosultam 10-2.
Scheme 24: Fluorination with N-fluorosultam 10-2.
Scheme 25: Synthesis of N-F reagent 11-2.
Scheme 26: Fluorination with N-F reagent 11-2.
Scheme 27: Synthesis and reaction of N-fluorolactams 12-1.
Scheme 28: Synthesis of NFOBS 13-2.
Scheme 29: Fluorination with NFOBS 13-2.
Scheme 30: Synthesis of NFSI (14-2).
Scheme 31: Fluorination with NFSI 14-2.
Scheme 32: Synthesis of N-fluorosaccharin (15-1) and N-fluorophthalimide (15-2).
Scheme 33: Synthesis of N-F salts 16-3.
Scheme 34: Fluorination with N-F salts 16-3.
Figure 3: Monofluorination with Selectfluor (16-3a).
Figure 4: Difluorination with Selectfluor (16-3a).
Scheme 35: Transfer fluorination of Selectfluor (16-3a).
Scheme 36: Fluorination of substrates with Selectfluor (16-3a).
Scheme 37: Synthesis of chiral N-fluoro-sultam 17-2.
Scheme 38: Asymmetric fluorination with chiral 17-2.
Figure 5: Synthesis of Zwitterionic N-fluoropyridinium salts 18-2a–h.
Scheme 39: Fluorinating power order of zwitterionic N-fluoropyridinium salts.
Scheme 40: Fluorination with zwitterionic 18-2.
Scheme 41: Activation of salt 18-2h with TfOH.
Scheme 42: Synthesis of NFTh, 19-2.
Scheme 43: Fluorination with NFTh, 19-2.
Scheme 44: Synthesis of 3-fluorobenzo-1,2,3-oxathiazin-4-one 2,2-dioxide (20-2).
Scheme 45: Fluorination with 20-2.
Scheme 46: Synthesis of N-F amide 21-3.
Scheme 47: Fluorination with N-F amide 21-2.
Scheme 48: Synthesis of N,N’-difluorodiazoniabicyclo[2.2.2]octane salts 22-1.
Scheme 49: One-pot synthesis of N,N’-difluoro-1,4-diazoniabicyclo[2.2.2]octane bistetrafluoroborate salt (22-1d...
Figure 6: Fluorination of anisole with 22-1a, d, e.
Scheme 50: Fluorination with N,N’-diF bisBF4 22-1d.
Scheme 51: Synthesis of bis-N-F reagents 23-1–5.
Scheme 52: Fluorination with 23-2, 4, 5.
Figure 7: Synthesis of N,N’-difluorobipyridinium salts 24-2.
Figure 8: Controlled fluorination of N,N’-diF 24-2.
Scheme 53: Fluorinating power of N,N’-diF salts 24-2 and N-F salt 5-4a.
Scheme 54: Fluorination reactions with SynfluorTM (24-2b).
Scheme 55: Additional fluorination reactions with SynfluorTM (24-2b).
Scheme 56: Synthesis of N-F 25-1.
Scheme 57: Fluorination of polycyclic aromatics with 25-1.
Scheme 58: Synthesis of 26-1 and dimethyl analog 26-2.
Scheme 59: Fluorination with reagents 26-1, 26-2, 1-1, and 26-3.
Scheme 60: Synthesis of N-F reagent 27-2.
Scheme 61: Synthesis of chiral N-F reagents 27-6.
Scheme 62: Synthesis of chiral N-F 27-7–9.
Scheme 63: Asymmetric fluorination with 27-6.
Scheme 64: Synthesis of chiral N-F reagents 28-3.
Scheme 65: Asymmetric fluorination with 28-3.
Scheme 66: Synthesis of chiral N-F reagents 28-7.
Figure 9: Asymmetric fluorination with 28-7.
Scheme 67: In situ formation of N-fluorinated cinchona alkaloids with SelectfluorTM.
Scheme 68: Asymmetric fluorination with N-F alkaloids formed in situ.
Scheme 69: Synthesis of N-fluorocinchona alkaloids with Selectfluor.
Scheme 70: Asymmetric fluorination with 30-1–4.
Scheme 71: Transfer fluorination from various N-F reagents.
Figure 10: Asymmetric fluorination of silyl enol ethers.
Scheme 72: Synthesis of N-fluoro salt 32-2.
Scheme 73: Reactivity of N-fluorotriazinium salt 32-2.
Scheme 74: Synthesis of bulky N-fluorobenzenesulfonimide NFBSI 33-3.
Scheme 75: Comparison of NFSI and NFBSI.
Scheme 76: Synthesis of p-substituted N-fluorobenzenesulfonimides 34-3.
Figure 11: Asymmetric fluorination with 34-3 and a chiral catalyst 34-4.
Scheme 77: 1,4-Fluoroamination with Selecfluor and a chiral catalyst.
Figure 12: Asymmetric fluoroamination with 35-5a, b.
Scheme 78: Synthesis of Selectfluor analogs 35-5a, b.
Scheme 79: Synthesis of chiral dicationic DABCO-based N-F reagents 36-5.
Scheme 80: Asymmetric fluorocyclization with chiral 36-5b.
Scheme 81: Synthesis of chiral 37-2a,b.
Scheme 82: Asymmetric fluorination with chiral 37-2a,b.
Scheme 83: Asymmetric fluorination with chiral 37-2b.
Scheme 84: Reaction of indene with chiral 37-2a,b.
Scheme 85: Synthesis of Me-NFSI, 38-2.
Scheme 86: Fluorination of active methine compounds with Me-NFSI.
Scheme 87: Fluorination of malonates with Me-NFSI.
Scheme 88: Fluorination of keto esters with Me-NFSI.
Scheme 89: Synthesis of N-F 39-3 derived from the ethylene-bridged Tröger’s base.
Scheme 90: Fluorine transfer from N-F 39-3.
Scheme 91: Fluorination with N-F 39-3.
Scheme 92: Synthesis of SelectfluorCN.
Scheme 93: Bistrifluoromethoxylation of alkenes using SelectfluorCN.
Figure 13: Synthesis of NFAS 41-2.
Scheme 94: Radical fluorination with different N-F reagents.
Scheme 95: Radical fluorination of alkenes with NFAS 41-2.
Scheme 96: Radical fluorination of alkenes with NFAS 41-2f.
Scheme 97: Decarboxylative fluorination with NFAS 41-2a,f.
Scheme 98: Fluorine plus detachment (FPD).
Figure 14: FPD values of representative N-F reagents in CH2Cl2 and CH3CN (in parentheses). Adapted with permis...
Scheme 99: N-F homolytic bond dissociation energy (BDE).
Figure 15: BDE values of representative N-F reagents in CH3CN. Adapted with permission from ref. [127]. Copyright 2...
Figure 16: Quantitative reactivity scale for popular N-F reagents. Adapted with permission from ref. [138], publish...
Scheme 100: SET and SN2 mechanisms.
Scheme 101: Radical clock reactions.
Scheme 102: Reaction of potassium enolate of citronellic ester with N-F reagents, 10-1, NFSI, and 8-1.
Scheme 103: Reaction of compound IV with Selectfluor (OTf) and NFSI.
Scheme 104: Reaction of TEMPO with Selecfluor.
