Fluorosulfonylation of arenediazonium tetrafluoroborates with Na2S2O5 and N-fluorobenzenesulfonimide

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Fluorosulfonylation of arenediazonium tetraﬂuoroborates with Na₂S₂O₅

and N-ﬂuorobenzenesulfonimide

Shuai Liu, Yangen Huang, Xiu-Hua Xu, Feng-Ling Qing

PII:

S0022-1139(20)30351-1

DOI:

https://doi.org/10.1016/j.jﬂuchem.2020.109653

FLUOR 109653

Reference:

To appear in:

Journal of Fluorine Chemistry

Received Date:

Revised Date:

Accepted Date:

24 August 2020

28 September 2020

Please cite this article as: Liu S, Huang Y, Xu X-Hua, Qing F-Ling, Fluorosulfonylation of

arenediazonium tetraﬂuoroborates with Na₂S₂O₅and N-ﬂuorobenzenesulfonimide, Journal of

Fluorine Chemistry (2020), doi: https://doi.org/10.1016/j.jﬂuchem.2020.109653

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Fluorosulfonylation of arenediazonium tetrafluoroborates with Na₂S₂O₅and N-

fluorobenzenesulfonimide

Shuai Liu^a, Yangen Huang^a, Xiu-Hua Xu^b, Feng-Ling Qing^a,b

^aCollege of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North

Renmin Lu, Shanghai 201620, China

^bKey Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai

Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Science,

345 Lingling Lu, Shanghai 200032, China

Tel.: 86-21-54925187; Fax: 86-21-64166128; E-mail: flq@mail.sioc.ac.c n

 Corresponding author. Tel.: +86 21 54925187; fax: +86 21 64166128.

E-mail address: flq@mail.sioc.ac.cn (F.-L. Qing).

Graphical Abstract

Highlights

 ·Transition-metal-free Sandmeyer-type fluorosulfonylation.

 ·An alternative approach to arenesulfonyl fluorides.

 ·Three-component reaction.

 ·Mild reaction conditions and broad functional group compatibility.

1

Abstract

A transition-metal-free Sandmeyer-type fluorosulfonylation reaction has been achieved by the three-

component reaction of arenediazonium tetrafluoroborates, Na₂S₂O₅, and N-fluorobenzenesulfonimide

(NFSI). The reaction proceeds through a radical tandem process, affording various arenesulfonyl fluorides

in moderate to high yields. This protocol not only provides a complement to the previous

fluorosulfonylation reactions, but also extends the applications of Sandmeyer reaction.

Keywords: Fluorosulfonylation; arenediazonium salts; sulfur dioxide insert; fluorination; transition-

metal-free; radical.

1. Introduction

Due to the fortuitous balance between reactivity and stability, arenesulfonyl fluorides have found

remarkable utility as intermediates in organic synthesis [1] and covalent probes in chemical biology [2].

Recently, considerable efforts have focused on new applications of sulfonyl fluorides ranging from

fluorinating reagents [3] to Sulfur(VI) Fluoride Exchange (SuFEx) click chemistry [4]. Up to now,

numerous synthetic approaches to arenesulfonyl fluorides have been reported starting from a myriad of

different starting materials. The traditional method involves the nucleophilic fluorination of arenesulfonyl

chlorides [5] (Scheme 1a). However, arenesulfonyl chlorides require harsh conditions to synthesize, thus

rendering this approach incompatible with many functional groups. To address this issue, alternative

fluorination methods have been developed using arenesulfonic acids [6], arenesulfonates [7],

arenesulfinates [8], arenesulfonamides [9], or arenesulfonyl hydrazides [10] as the substrates (Scheme

1b). Arenesulfonyl fluorides could also be prepared from the corresponding thiols [11a], thioethers [11b],

or disulfides [11c,d] through oxidation and fluorination (Scheme 1c). Very recently, Noël and coworkers

developed an oxidant-free electrochemical process to generate arenesulfonyl fluorides from aryl thiols or

2

disulfides [12] (Scheme 1d). Comparing to the above transformations from sulfur-containing compounds,

the direct fluorosulfonylation of easily available aromatic substrates is more attractive. In this context,

Sammis and Ball reported the electrophilic fluorosulfonylation of aryl Grignard reagents with sulfuryl

fluoride (SO₂F₂) [13] (Scheme 1e). Kim and Kwon also reported the synthesis amino-substituted

arenesulfonyl fluorides by the three-component reaction of aryne precursors, secondary amines, and

SO₂F₂[14] (Scheme 1f). In 2017, the groups of Willis and Bagley [15a] as well as Ball [15b] respectively

developed the one-pot synthesis of arenesulfonyl fluorides from the corresponding aryl halides, through

palladium-catalyzed sulfonylation of aryl halides using DABSO as an SO₂source followed by in situ

treatment of the resultant sulfinate with the electrophilic fluorine source NFSI or selectfluor (Scheme 1g).

Willis disclosed a similar strategy employing copper- or nickel-catalyzed sulfination and electrophilic

fluorination for the conversion of aryl boronic acids to arenesulfonyl fluorides [16] (Scheme 1h). Despite

these elegant achievements, the development of new synthetic methods using easily available substrates

and simple reagents is still highly desirable.

Scheme 1 Synthetic approaches to arenesulfonyl fluorides

3

The Sandmeyer reaction is widely used for the preparation of functionalized arenes from aryl

diazonium salts, which are easily accessible from commercially available anilines. In organofluorine

chemistry, the Sandmeyer-type reactions have proven to be an efficient strategy to introduce F atom [17]

and fluorine-containing groups such as CF₃[18], SCF₃[19], and OCF₃[20] into the aromatic rings. In

2015, our group also reported a copper-promoted tunable trifluoromethanesulfonylation and

trifluoromethylation of arenediazonium tetrafluoroborates with NaSO₂CF₃[21]. To the best of our

knowledge, the Sandmeyer-type fluorosulfonylation had not been reported before we started this work.

In 2016, Wu and co-workers discovered that the reaction of the SO₂surrogate of DABCO·(SO₂)₂

and aryldiazonium tetrafluoroborates would provide an arenesulfonyl radical, which then underwent

further transformations for the synthesis of 3-sulfonated coumarins [22]. Recently, the combination of

4

arenediazonium salts and a SO₂surrogate, DABCO·(SO₂)₂[23] or inorganic sulfites [24], have been

widely applied in the synthesis of arenesulfonyl-containing compounds. Inspired these achievements, we

envisioned that arenesulfonyl fluorides might be constructed starting from aryldiazonium salts, SO₂

surrogates, and F sources via arenesulfonyl radical intermediates. Herein, we disclose a transition-metal-

free fluorosulfonylation of arenediazonium tetrafluoroborates with Na₂S₂O₅and NFSI for the preparation

of arenesulfonyl fluorides (Scheme 1i). Notably, during the preparation of this manuscript, the analogous

fluorosulfonylation of arenediazonium salts have been reported using different SO₂and F sources [25].

2. Results and Discussion

To test our hypothesis, 4-methoxybenzenediazonium tetrafluoroborate (1a) was chosen as the model

substrate to optimize fluorosulfonylation reaction conditions (Table 1). To our delight, the reaction of 1a

with Na₂S₂O₅as the SO₂source and N-fluorobenzenesulfonimide (NFSI) as the F source in MeOH at 40

^oC afforded the fluorosulfonylated product 2a in 39% yield (entry 1). The screening of solvents revealed

that MeCN was superior, affording 2a in 54% yield (entries 2 and 3). Slightly higher yields were observed

when small amounts of water were added (entries 4 and 5). However, further increasing the amount of

water resulted in a decreased yield of 2a (entry 6). Subsequently, different SO₂sources including K₂S₂O₅

and DABCOSO₂were examined, but no better result was obtained (entries 7 and 8). Switching the F

source from NFSI to selectfluor led to diminished yield (entry 9), whereas the use of KF as the F source

could not deliver the desired product (entry 10). Finally, the reaction temperature was explored, and 60

^oC was found to be optimal, furnishing 2a in 74% yield (entries 11-13). Notably, methoxybenzene was

the main by-product of this reaction.

Table 1. Optimization of reaction conditions.^a

5

Entry

SO₂source

F source

Solvent

Temperature Yield (%)^b

MeOH

1

Na₂S₂O₅

K₂S₂O₅

NFSI

40 ^oC

rt

39

trace

54

59

58

47

49

23

28

0

DMF

2

MeCN

3

4

MeCN/H₂O = 2/0.1

MeCN/H₂O = 2/0.02

MeCN/H₂O = 2/0.2

MeCN/H₂O = 2/0.1

5

6

7

DABCOSO₂

Na₂S₂O₅

8

9

Selectfluor MeCN/H₂O = 2/0.1

10

11

12

13

KF

MeCN/H₂O = 2/0.1

NFSI

26

74

70

60 ^oC

80 ^oC

^aReaction conditions: 1a (0.1 mmol), SO₂Source (0.2 mmol), F Source (0.15 mmol), solvent (2.0 mL), temperature, under N₂, 6 h_.

^bYields were determined by ¹⁹F NMR spectroscopy using trifluoromethylbenzene as an internal standard.

With the optimized reaction conditions (Table 1, entry 12) in hand, the substrate scope of transition-

metal-free fluorosulfonylation of arenediazonium salts was investigated. Arenediazonium salts (1a-1j)

bearing either electron-donating or electron-withdrawing substituents reacted smoothly to give the

corresponding arenesulfonyl fluorides in moderate to high yields. Notably, the fluoro- and bromo-

containing substrates (1g and 1h) are suitable substrates for the reaction, enabling further

functionalization. Di- and trisubstituted arenediazonium salts 1k and 1l were also compatible under the

standard reaction conditions. Substrates bearing relatively bulky naphthyl group (1m and 1n) proceeded

efficiently to afford the desired products in good yields. Heteroaryl substrates including quinoline (1o),

benzothiazole (1p and 1q), and carbazole (1r) derivatives were smoothly converted to the desired

products. However, the reaction of pyridyl diazonium salts resulted in the corresponding products in low

yields.

Table 2. Scope of aryldiazonium tetrafluoroborates.^a

6

^aReaction conditions: 1 (0.2 mmol), Na₂S₂O₅(0.4 mmol), NFSI (0.3 mmol), MeCN/H₂O (4.0/0.2 mL), 60 ^oC,_,under N₂, 6 h, isolated

yields.

Remarkably, in

a

representative attempt, 4-methoxyaniline was converted into 4-

methoxybenzenesulfonyl fluoride (2a) in a one-pot procedure (Scheme 2), albeit in somewhat lower yield

than that in the standard protocol (Table 2). Furthermore, when the aliphatic amines were subjected to

this one-pot reaction, none of the desired product could be detected.

Scheme 2 One-pot fluorosulfonylation of 4-methoxyaniline

7

In order to understand the reaction mechanism, a typical radical scavenger, 2,2,6,6-tetramethyl-1-

piperidinyloxy (TEMPO), was added to the standard reaction of 1a (Scheme 3a). None of the desired

product 2a was formed, whereas the TEMPO-trapped product could be detected by GC-MS (see the

supporting information). These results indicated that a radical process was probably involved in this

reaction. On the basis of this result and previous reports [24,25], a plausible reaction mechanism was

proposed in Scheme 3b. Initially, aryldiazonium salts 1 undergoes a single electron transfer (SET)

reduction to generate aryl radical A. Then, aryl radical A reacts with SO₂in Na₂S₂O₅, affording the

arenesulfonyl radical B. Finally, fluorine atom transfer from NFSI to arenesulfonyl radical B furnishes

the desired arenesulfonyl fluorides 2. In accordance with the fluorosulfonylation reaction reported by

Weng [25b], Na₂S₂O₅probably acts as both of the reductant and SO₂source in this reaction.

Scheme 3 Mechanistic investigation

3. Conclusion

8

In conclusion, we have developed an alternative approach to arenesulfonyl fluorides through the three-

component reaction of readily available arenediazonium tetrafluoroborates, Na₂S₂O₅, and NFSI. Unlike

the classic Sandmeyer reaction, this reaction proceeds under copper-free conditions. The mild conditions

allow the tolerance of a variety of functional groups and heterocycles. Further extension of the

applications of Sandmeyer reaction in the synthesis of other valuable fluorine-containing compounds are

currently in progress.

4. Experimental Section

4.1. General information

¹H NMR (TMS as the internal standard), ¹³C NMR, and ¹⁹F NMR spectra (CFCl₃as the outside standard

and low field is positive) were recorded on a 400 or 600 MHz spectrometer. Chemical shifts (δ) are

reported in ppm, and coupling constants (J) are in Hertz (Hz). The following abbreviations were used to

explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet. HRMS data using

EI were obtained on a GC/MS TOF high resolution mass spectrometer equipped with a liquid

chromatography system. All reagents were used as received from commercial sources without further

purification or prepared as described in references. Substrates were prepared in accordance with methods

described in the reference [26].

4.2. Typical procedure of the preparation for arenediazonium tetrafluoroborates

Method A: In a 100 mL round-bottom flask, the aniline (20 mmol) was dissolved in a mixture of H₂O (10

mL) and HBF₄(48% aq, 6 mL). After stirring for 15 minutes, the solution of NaNO₂(1.5 g, 1.1 equiv., in

4.0 mL H₂O) was added dropwise at 0 ^oC. The mixture was stirred for another 30 minutes at 0 ^oC. Then,

the arenediazonium tetrafluoroborate was removed by filtration and washed successively twice with Et₂O.

The crude product was dried in vacuo for 20 minutes and was then directly used without further

purification.

9

Method B: In a 100 mL round-bottom flask, the aniline (20 mmol) was dissolved in a mixture of ethanol

(8.0 mL) and HBF₄(48% aq, 6.0 mL). Subsequently, tert-butyl nitrite (4.7 mL, 2.0 equiv.) was added

dropwise to the solution at 0 °C. The reaction mixture was stirred for 30 minutes at 0 °C, and anhydrous

Et₂O was added to precipitate the corresponding arenediazonium tetrafluoroborate. The solid was filtered

off and washed twice with Et₂O. The obtained arenediazonium tetrafluoroborate was dried in vacuo for

20 minutes and was then directly used without further purification.

Substrates 1a, 1b, 1c, 1d, 1f, 1h, 1i, 1j, 1l, 1m, 1n, and 1q were prepared according to method A.

Substrates 1e, 1g, 1k, 1o, 1p, and 1r were prepared according to method B.

4.3. General procedures for fluorosulfonylation of aryldiazonium tetrafluoroborates

To a mixture of arenediazonium tetrafluoroborate (0.2 mmol, 1.0 equiv.) and NFSI (94.5 mg, 0.3 mmol,

1.5 equiv.) in MeCN/H₂O (4.0/0.2 mL) was added Na₂S₂O₅(76.0 mg, 0.4 mmol, 2.0 equiv.). The reaction

o

mixture was stirred at 60 C under nitrogen atmosphere for 6 h. After the reaction was complete, brine

was added. The resulting mixture was extracted with EtOAc for three times. The combined organic layer

was washed with brine, dried over anhydrous Na₂SO₄, and concentrated under reduced pressure. The

resulting residue was purified by silica gel flash column chromatography to give the product.

4.3.1. 4-Methoxybenzenesulfonyl fluoride (2a). After purification by silica gel column chromatography

(cyclohexane/EtOAc = 10:1), compound 2a was obtained as a yellow oil (26.2 mg, 69%). ¹H NMR (400

19

MHz, CDCl₃) δ 7.87 (d, J = 8.6 Hz, 2H), 6.99 (d, J = 8.6 Hz, 2H), 3.85 (s, 3H). F NMR (565 MHz,

CDCl₃) δ 67.29 (s, 1F). ¹³C NMR (151 MHz, CDCl₃) δ 165.2, 130.9, 124.1 (d, J = 24.7 Hz), 114.9, 55.9.

The spectroscopic data were consistent with those previously published [15a].

4.3.2. 4-Methylbenzenesulfonyl fluoride (2b). After purification by silica gel column chromatography

(cyclohexane/EtOAc = 99:1), compound 2b was obtained as a white solid (24.4 mg, 70%). Mp 41-42 ^oC.

¹H NMR (400 MHz, CDCl₃) δ 7.82 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 2.42 (s, 3H). ¹⁹F NMR

(565 MHz, CDCl₃) δ 66.29 (s, 1F). ¹³C NMR (151 MHz, CDCl₃) δ 147.1, 130.3, 130.1 (d, J = 24.2 Hz),

10

128.5, 21.9. The spectroscopic data were consistent with those previously published [15a].

4.3.3. 4-(Tert-butyl)benzenesulfonyl fluoride (2c). After purification by silica gel column chromatography

(cyclohexane/EtOAc = 99:1), compound 2c was obtained as a white solid (26.4 mg, 61%). Mp 64-66 ^oC.

¹H NMR (400 MHz, CDCl₃) δ 7.86 (d, J = 8.6 Hz, 2H), 7.56 (d, J = 8.3 Hz, 2H), 1.30 (s, 9H). ¹⁹F NMR

(565 MHz, CDCl₃) δ 66.21 (s, 1F). ¹³C NMR (151 MHz, CDCl₃) δ 159.9, 130.0 (d, J = 24.2 Hz), 128.4,

126.7, 35.6, 31.0. The spectroscopic data were consistent with those previously published [12].

4.3.4. [1,1'-Biphenyl]-4-sulfonyl fluoride (2d). After purification by silica gel column chromatography

(cyclohexane/EtOAc = 10:1), compound 2d was obtained as a white solid (20.3 mg, 43%). Mp 78-79 ^oC.

¹H NMR (600 MHz, CDCl₃) δ 8.11 (d, J = 8.4 Hz, 2H), 7.85 (d, J = 8.3 Hz, 2H), 7.65 (d, J = 7.3 Hz, 2H),

7.55 (t, J = 7.4 Hz, 2H), 7.50 (t, J = 7.2 Hz, 1H). ¹⁹F NMR (565 MHz, CDCl₃) δ 66.53 (s, 1F). ¹³C NMR

(151 MHz, CDCl₃) δ 148.7, 138.5, 131.4 (d, J = 24.5 Hz), 129.3, 129.2, 129.0, 128.2, 127.5. The

spectroscopic data were consistent with those previously published [15a].

4.3.5. Ethyl 4-(fluorosulfonyl)benzoate (2e). After purification by silica gel column chromatography

(cyclohexane/EtOAc = 10:1), compound 2e was obtained as a white solid (27.1 mg, 58%). Mp 36-38 ^oC.

¹H NMR (600 MHz, CDCl₃) δ 8.31 (d, J = 8.3 Hz, 2H), 8.11 (d, J = 8.5 Hz, 2H), 4.47 (q, J = 7.1 Hz, 2H),

19

13

1.45 (t, J = 7.1 Hz, 3H). F NMR (565 MHz, CDCl₃) δ 65.82 (s, 1F). C NMR (151 MHz, CDCl₃) δ

164.4, 136.9, 136.6 (d, J = 25.3 Hz), 130.7, 128.5, 62.2, 14.2. The spectroscopic data were consistent with

those previously published [15a].

4.3.6. 3-Cyanobenzenesulfonyl fluoride (2f). After purification by silica gel column chromatography

(cyclohexane/EtOAc = 10:1), compound 2f was obtained as an orange solid (26.4 mg, 72%). Mp 48-50

^oC. ¹H NMR (400 MHz, CDCl₃) δ 8.35-8.12 (m, 2H), 8.01 (d, J = 7.7 Hz, 1H), 7.77 (t, J = 7.9 Hz, 1H).

13

¹⁹F NMR (565 MHz, CDCl₃) δ 66.33 (s, 1F). C NMR (101 MHz, CDCl₃) δ 137.6, 133.7 (d, J = 27.2

Hz), 131.2, 131.0, 129.9, 115.2, 113.7. MS (EI): m/z 185 M⁺. HRMS (ESI-TOF): m/z Calculated for

C₇H₄FNO₂S M⁺:184.9947; Found: 184.9941.

11

4.3.7. 4-Fluorobenzenesulfonyl fluoride (2g). After purification by silica gel column chromatography

1

(cyclohexane/EtOAc = 99:1), compound 2g was obtained as a colourless oil (25.6 mg, 72%). H NMR

(600 MHz, CDCl₃) δ 8.09-8.07 (m, 2H), 7.35 (t, J = 8.4 Hz, 2H). ¹⁹F NMR (565 MHz, CDCl₃) δ 66.79 (s,

1F), -99.28 to -99.32 (m, 1F). ¹³C NMR (151 MHz, CDCl₃) δ 166.9 (d, J = 259.9 Hz), 131.6 (d, J = 10.3

Hz), 129.0 (dd, J = 25.7, 3.4 Hz), 117.3 (d, J = 23.2 Hz). The spectroscopic data were consistent with

those previously published [15a].

4.3.8. 3-Bromobenzenesulfonyl fluoride (2h). After purification by silica gel column chromatography

1

(cyclohexane/EtOAc = 10:1), compound 2h was obtained as a colorless oil (33.9 mg, 71%). H NMR

(600 MHz, CDCl₃) δ 8.18 (t, J = 1.9 Hz, 1H), 7.99 (d, J = 9.0 Hz, 1H), 7.94 (d, J = 7.3 Hz, 1H), 7.55 (t,

J = 8.0 Hz, 1H). ¹⁹F NMR (565 MHz, CDCl₃) δ 66.26 (s, 1F). ¹³C NMR (151 MHz, CDCl₃) δ 138.7, 134.7

(d, J = 25.5 Hz), 131.3, 131.1, 127.0, 123.6. The spectroscopic data were consistent with those previously

published [25b].

4.3.9. 4-(Trifluoromethyl)benzenesulfonyl fluoride (2i). After purification by silica gel column

chromatography (cyclohexane/EtOAc = 99:1), compound 2i was obtained as a white solid (30.0 mg,

68%). Mp 44-46 ^oC. ¹H NMR (400 MHz, CDCl₃) δ 8.09 (d, J = 8.3 Hz, 2H), 7.84 (d, J = 8.2 Hz, 2H). ¹⁹F

NMR (565 MHz, CDCl₃) δ 65.75 (s, 1F), -63.62 (s, 3F). ¹³C NMR (151 MHz, CDCl₃) δ 137.2 (q, J = 33.6

Hz), 136.5 (d, J = 25.9 Hz), 129.1, 126.9 (q, J = 3.7 Hz), 122.7 (q, J = 273.5 Hz). The spectroscopic data

were consistent with those previously published [12].

4.3.10. 4-(Trifluoromethoxy)benzenesulfonyl fluoride (2j). After purification by silica gel column

chromatography (cyclohexane/EtOAc = 20:1), compound 2j was obtained as a brown oil (26.8 mg, 55%).

¹H NMR (400 MHz, CDCl₃) δ 8.09 (d, J = 8.9 Hz, 2H), 7.46 (d, J = 8.5 Hz, 2H). ¹⁹F NMR (565 MHz,

CDCl₃) δ 66.57 (s, 1F), -57.71 (s, 3F). ¹³C NMR (151 MHz, CDCl₃) δ 154.3, 131.1, 130.9, 128.6, 125.4

(t, J = 6.2 Hz), 121.2, 120.1 (q, J = 260.8 Hz). The spectroscopic data were consistent with those

previously published [10].

12

4.3.11. Benzo[d][1,3]dioxole-5-sulfonyl fluoride (2k). After purification by silica gel column

chromatography (cyclohexane/EtOAc = 8:1), compound 2k was obtained as a white solid (29.8 mg, 73%).

Mp 71-72 ^oC. ¹H NMR (600 MHz, CDCl₃) δ 7.63 (dd, J = 8.3, 1.5 Hz, 1H), 7.39 (d, J = 1.8 Hz, 1H), 6.99

(d, J = 8.1 Hz, 1H), 6.18 (s, 2H).¹⁹F NMR (565 MHz, CDCl₃) δ 66.84 (s, 1F).¹³C NMR (151 MHz, CDCl₃)

δ 153.9, 148.7, 125.6 (d, J = 25.0 Hz), 125.2, 108.8, 108.2, 103.0. The spectroscopic data were consistent

with those previously published [15a].

4.3.12. 3,4,5-Trimethoxybenzenesulfonyl fluoride (2l). After purification by silica gel column

chromatography (cyclohexane/EtOAc = 50:1), compound 2l was obtained as a white solid (26.0 mg,

52%). Mp 76-78 ^oC. ¹H NMR (600 MHz, CDCl₃) δ 7.23 (s, 2H), 3.97 (s, 3H), 3.96 (s, 6H). ¹⁹F NMR (565

MHz, CDCl₃) δ 66.65 (s, 1F). ¹³C NMR (151 MHz, CDCl₃) δ 153.6, 144.1, 126.9 (d, J = 24.7 Hz), 105.8,

61.1, 56.6. The spectroscopic data were consistent with those previously published [25b].

4.3.13. Naphthalene-1-sulfonyl fluoride (2m). After purification by silica gel column chromatography

(cyclohexane/EtOAc = 50:1), compound 2m was obtained as a colourless oil (33.6 mg, 80%). ¹H NMR

(600 MHz, CDCl₃) δ 8.58 (dd, J = 8.6, 2.4 Hz, 1H), 8.40 (d, J = 7.4 Hz, 1H), 8.26 (d, J = 8.2 Hz, 1H),

8.03 (d, J = 8.2 Hz, 1H), 7.84-7.76 (m, 1H), 7.75-7.68 (m, 1H), 7.68-7.59 (m, 1H). ¹⁹F NMR (565 MHz,

CDCl₃) δ 62.58 (s, 1F). ¹³C NMR (151 MHz, CDCl₃) δ 136.9, 134.1, 131.10, 131.09, 129.5, 129.1, 128.3,

127.8, 124.2, 124.1. The spectroscopic data were consistent with those previously published [15a].

4.3.14. 5-Bromonaphthalene-1-sulfonyl fluoride (2n). After purification by silica gel column

chromatography (cyclohexane/EtOAc = 8:1), compound 2n was obtained as a yellow solid (43.9 mg,

o

1

76%). Mp 58-62 C. H NMR (400 MHz, CDCl₃) δ 8.71 (d, J = 8.4 Hz, 1H), 8.53 (d, J = 8.6 Hz, 1H),

8.43 (d, J = 7.4 Hz, 1H), 7.97 (d, J = 7.5 Hz, 1H), 7.72 (t, J = 8.0 Hz, 1H), 7.60 (t, J = 8.1 Hz, 1H). ¹⁹F

13

NMR (565 MHz, CDCl₃) δ 63.18 (s, 1F). C NMR (151 MHz, CDCl₃) δ 136.0, 132.6, 132.0, 131.87,

131.86, 129.7, 129.6, 129.54, 125.4, 124.0, 123.9. MS (EI): m/z 288 M⁺; HRMS (ESI-TOF): m/z

Calculated for C₁₀H₆BrFO₂S M⁺: 287.9256; Found: 287.9250.

13

4.3.15. Quinoline-6-sulfonyl fluoride (2o). After purification by silica gel column chromatography

(cyclohexane/EtOAc = 50:1), compound 2o was obtained as a white solid (21.1 mg, 50%). Mp 80-82 ^oC.

¹H NMR (600 MHz, CDCl₃) δ 9.18 (dd, J = 4.3, 1.7 Hz, 1H), 8.65 (d, J = 2.1 Hz, 1H), 8.43-8.32 (m, 2H),

8.21 (dd, J = 8.9, 2.2 Hz, 1H), 7.66 (dd, J = 8.3, 4.2 Hz, 1H). ¹⁹F NMR (565 MHz, CDCl₃) δ 66.41 (s, 1F).

¹³C NMR (101 MHz, CDCl₃) δ 154.5, 150.3, 137.6, 132.0, 131.1, 130.7 (d, J = 25.5 Hz), 127.2, 126.0,

123.3. The spectroscopic data were consistent with those previously published [25b].

4.3.16. Benzo[d]thiazole-5-sulfonyl fluoride (2p). After purification by silica gel column chromatography

(cyclohexane/EtOAc = 10:1), compound 2p was obtained as a white solid (22.9 mg, 53%). Mp 102-104

^oC. ¹H NMR (400 MHz, CDCl₃) δ 9.26 (s, 1H), 8.83 (s, 1H), 8.26 (d, J = 8.4 Hz, 2H), 8.07 (d, J = 8.4 Hz,

19

2H). F NMR (377 MHz, CDCl₃) δ 67.38 (s, 1F). ¹³C NMR (101 MHz, CDCl₃) δ 157.5, 152.9, 141.4,

131.1 (d, J = 25.3 Hz), 124.7, 123.9, 123.6. The spectroscopic data were consistent with those previously

published [25b].

4.3.17. 2-Methylbenzo[d]thiazole-5-sulfonyl fluoride (2q). After purification by silica gel column

chromatography (cyclohexane/EtOAc = 10:1), compound 2q was obtained as a white solid (37.4 mg,

o

1

81%). Mp 62-64 C. H NMR (600 MHz, CDCl₃) δ 8.61 (d, J = 1.8 Hz, 1H), 8.10 (d, J = 8.4 Hz, 1H),

7.97 (dd, J = 8.5, 1.8 Hz, 1H), 2.94 (s, 3H). ¹⁹F NMR (565 MHz, CDCl₃) δ 67.33 (s, 1F). ¹³C NMR (101

MHz, CDCl₃) δ 170.9, 153.0, 143.5, 130.6 (d, J = 24.9 Hz), 123.2, 123.1, 122.9, 20.5. MS (EI): m/z 231

M⁺; HRMS (ESI-TOF): m/z Calculated for C₈H₆FNO₂S₂M⁺: 230.9824; Found: 230.9818.

4.3.18. 9-Ethyl-9H-carbazole-3-sulfonyl fluoride (2r). After purification by silica gel column

chromatography (cyclohexane/EtOAc = 20:1), compound 2r was obtained as a brown solid (33.2 mg,

60%). Mp 98-100 ^oC. ¹H NMR (400 MHz, CDCl₃) δ 8.77 (s, 1H), 8.17 (d, J = 7.6 Hz, 1H), 8.08 (d, J =

8.7 Hz, 1H), 7.63 (t, J = 7.3 Hz, 1H), 7.58-7.52 (m, 2H), 7.40 (t, J = 7.1 Hz, 1H), 4.44 (q, J = 6.5 Hz 2H),

13

1.50 (t, J = 6.6 Hz, 3H). ¹⁹F NMR (377 MHz, CDCl₃) δ 69.22 (s, 1F). C NMR (101 MHz, CDCl₃) δ

143.2, 140.9, 127.7, 125.4, 123.1, 122.3, 122.2, 121.7 (d, J = 23.5 Hz), 121.1, 121.0, 109.5, 109.0, 38.1,

14

13.8. MS (EI): m/z 277 M⁺; HRMS (EI-TOF): m/z Calculated for C₁₄H₁₂FNO₂S [M+H]⁺: 277.0573; Found:

277.0567.

4.4. One-pot fluorosulfonylation of 4-methoxyaniline

In a 25 mL round-bottom flask, 4-methoxyaniline (61.6 mg, 0.5 mmol) was dissolved in a mixture of

ethanol (2.0 mL) and HBF₄(132 μL, aq. 48%, 1.0 mmol). Subsequently, tert-butyl nitrite (135 μL, 1.0

mmol) was added dropwise to the solution at 0 °C. The reaction mixture was stirred for 30 minutes at

room temperature, then Na₂S₂O₅(190.1 mg, 1.0 mmol) and NFSI (236.5 mg, 0.75 mmol) were added

o

successively. The reaction mixture was stirred at 60 C under nitrogen atmosphere for 6 h. After the

reaction was complete, brine was added. The resulting mixture was extracted with EtOAc for three times.

The combined organic layer was washed with brine, dried over anhydrous Na₂SO₄, and concentrated

under reduced pressure. The resulting residue was purified by silica gel flash column chromatography

(cyclohexane/EtOAc = 10:1) to give 2a as a yellow oil (57.3 mg, 60%).

Declaration of interests

The authors declare that they have no known competing financial interests or personal relationships that

could have appeared to influence the work reported in this paper.

Acknowledgement

We thank National Natural Science Foundation of China (21421002, 21991211) and the Strategic Priority

Research Program of the Chinese Academy of Sciences (XDB20000000) for funding this work.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in the online version, at

http://dx.doi.org/10.1016/j. jfluchem.xxxx.xx.xxx.

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Article Doi

Fluorosulfonylation of arenediazonium tetrafluoroborates with Na2S2O5 and N-fluorobenzenesulfonimide

DOI: 10.1016/j.jfluchem.2020.109653

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