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. 2024 Feb 13;29(4):831. doi: 10.3390/molecules29040831

Hydroxylation of Aryl Sulfonium Salts for Phenol Synthesis under Mild Reaction Conditions

Xuan-Bo Hu 1, Qian-Qian Fu 1, Xue-Ying Huang 1, Xue-Qiang Chu 1, Zhi-Liang Shen 1,*, Chengping Miao 2,*, Weiyi Chen 3,*
Editor: Ana Margarida Gomes Silva
PMCID: PMC10891898  PMID: 38398583

Abstract

Hydroxylation of aryl sulfonium salts could be realized by utilizing acetohydroxamic acid and oxime as hydroxylative agents in the presence of cesium carbonate as a base, leading to a variety of structurally diverse hydroxylated arenes in 47–95% yields. In addition, the reaction exhibited broad functionality tolerance, and a range of important functional groups (e.g., cyano, nitro, sulfonyl, formyl, keto, and ester) could be well amenable to the mild reaction conditions.

Keywords: hydroxylation, phenol synthesis, aryl sulfonium salts, acetohydroxamic acid, oxime

1. Introduction

Phenols and their derivatives are not only important building blocks in modern organic synthesis, but also structural units which are ubiquitously present in natural products, biologically and pharmaceutically active molecules, and functional materials [1]. As a consequence, the development of effective methodologies for the preparation of phenols has attracted considerable attention from the synthetic community. In addition to the classic methods developed in order to access phenols by virtue of Sandmeyer reactions and direct arene oxidation [2,3,4,5,6,7,8,9,10], the transition-metal-catalyzed hydroxylation of aryl halides has also been proven to be one of the most efficient methods by which to synthesize phenol [11,12,13,14,15,16,17]. A range of hydroxide sources and their surrogates, such as alkali metal hydroxide (MOH) [18,19,20,21], water [22,23,24,25,26,27], boric acid [28], molecular oxygen [29,30], silanol [31], hydrogen peroxide [31], and nitrous oxide [32,33], have been revealed to be effective for the hydroxylation of aryl halides and its variants (Scheme 1a). In 2016 and 2017, the group of Fier and Maloney originally disclosed that benzaldoxime [34,35,36,37] and acetohydroxamic acid [38] could also function as effective hydroxylating agents for the conversion of aryl halides to phenols (Scheme 1b). In 2021, James et al. found that electron-rich pyrrole-based oxime is more efficient than benzaldoxime for the hydroxylation of aryl halides [39].

Recently, the development of alternative electrophiles [40,41,42,43,44,45,46,47] as substitutes for conventional aryl halides in hydroxylative reactions have aroused considerable attention in the field of synthetic organic chemistry (Scheme 1c) [48,49,50]. For instance, Cornella et al. have described how pyridinium salts generated in situ from the reaction of aminoheterocycles with pyrylium tetrafluoroborate salts could be converted into their hydroxylated analogue by utilizing acetohydroxamic acid as a hydroxyl source [48]. James et al. have demonstrated that nitroarenes could also be effectively transformed into phenols via a denitrative functionalization protocol that employs their previously developed pyrrole-based oxime as hydroxylating agent under transition-metal-free conditions [49]. Cheng and Ye have reported that aryl ammonium salts could also efficiently undergo hydroxylation by using benzaldoxime and acetohydroxamic acid as hydroxide surrogates [50]. In recent decades, readily accessible and shelf-stable organosulfonium salts have also been proven to be versatile electrophiles for undergoing a broad range of organic transformations [51,52,53,54,55,56,57,58,59,60,61,62,63,64,65,66,67,68,69,70,71,72,73]. Although the hydroxylation of aryl thianthrenium salts have been accomplished by using water as hydroxide source, the reaction should be conducted under photoredox conditions in the presence of Ir and Cu catalysts [74]. In the continuation of our efforts to develop efficient organic transformations with the use of alternative electrophiles [75,76,77,78,79,80,81,82,83,84] under mild reaction conditions, herein we report a hydroxylation of aryl sulfonium salts by using acetohydroxamic acid and oxime as hydroxylative agents, which enabled the efficient assembly of hydroxylated arenes in modest-to-good yields with good functional group compatibility (Scheme 1d).

Scheme 1.

Scheme 1

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Hydroxylation of aryl halides and their counterparts. (a) Hydroxylation of aryl halides by using various hydroxide sources [11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33]; (b) Hydroxylation of aryl halides by using oxime and acetohydroxamic acid [34,35,36,37,38,39]; (c) Hydroxylation of other aryl electrophiles by using oxime and hydroxamic acid [48,49,50]; (d) Hydroxylation of aryl sulfonium salts by using oxime and hydroxamic acid (this work).

2. Results

Initially, we sought to optimize the reaction conditions for the hydroxylation of (4-cyanophenyl)dimethylsulfonium-trifluoromethanesulfonate (1a) by using N-hydroxyacetamide (2a) as a hydroxylating agent [38] in the co-existence of various bases and solvents. Among the different organic bases and inorganic bases surveyed and outlined in Table 1 (entries 1–11), Cs2CO3 emerged as the base of choice (entry 8), leading to the corresponding phenol 3a in 66% NMR yield when the reaction was carried out in DMSO (1 mL) at 80 °C for 18 h. Subsequent screening of other reaction media, including DMF, 1,4-dioxane, NMP, MeCN, toluene, THF, and H2O (entries 12–18), did not further enhance the reaction performance. Conducting the reaction at different temperatures (60 °C and 100 °C, entries 19–20) also made no significant difference. Gratifyingly, the NMR yield of product 3a could be further improved to 81% by using 2 mL DMSO as solvent (entry 21). In addition, evaluation of other reaction parameters, including the amount of Cs2CO3 (3 equiv. or 7 equiv., entries 22–23), reaction time (12 h or 24 h, entries 24–25), equivalents of N-hydroxyacetamide 2a (2 equiv. or 4 equiv., entries 26–27), and the amount of DMSO (4 mL, entry 28), were performed. However, in most cases, variation of the reaction conditions either led to decreased product yield or produced a comparable result to that of entry 21.

Table 1.

Optimization of reaction conditions a.

graphic file with name molecules-29-00831-i001.jpg
Entry 2a (x equiv.) Base
(y equiv.)		 Solvent
(z mL)		 Temp.
(°C)		 Time (h) Yield (%) b
1 3 equiv. DBU (5 equiv.) DMSO (1 mL) 80 °C 18 h 9
2 3 equiv. DABCO (5 equiv.) DMSO (1 mL) 80 °C 18 h <5
3 3 equiv. CsF (5 equiv.) DMSO (1 mL) 80 °C 18 h 31
4 3 equiv. NaOAc (5 equiv.) DMSO (1 mL) 80 °C 18 h <5
5 3 equiv. K3PO4 (5 equiv.) DMSO (1 mL) 80 °C 18 h 27
6 3 equiv. Na2CO3 (5 equiv.) DMSO (1 mL) 80 °C 18 h 10
7 3 equiv. K2CO3 (5 equiv.) DMSO (1 mL) 80 °C 18 h 52
8 3 equiv. Cs2CO3 (5 equiv.) DMSO (1 mL) 80 °C 18 h 66
9 3 equiv. KOH (5 equiv.) DMSO (1 mL) 80 °C 18 h 40
10 3 equiv. tBuOK (5 equiv.) DMSO (1 mL) 80 °C 18 h 6
11 3 equiv. LDA (5 equiv.) DMSO (1 mL) 80 °C 18 h 11
12 3 equiv. Cs2CO3 (5 equiv.) DMF (1 mL) 80 °C 18 h 53
13 3 equiv. Cs2CO3 (5 equiv.) 1,4-dioxane (1 mL) 80 °C 18 h 11
14 3 equiv. Cs2CO3 (5 equiv.) NMP (1 mL) 80 °C 18 h 56
15 3 equiv. Cs2CO3 (5 equiv.) MeCN (1 mL) 80 °C 18 h 24
16 3 equiv. Cs2CO3 (5 equiv.) toluene (1 mL) 80 °C 18 h 6
17 3 equiv. Cs2CO3 (5 equiv.) THF (1 mL) 80 °C 18 h 5
18 3 equiv. Cs2CO3 (5 equiv.) H2O (1 mL) 80 °C 18 h <5
19 3 equiv. Cs2CO3 (5 equiv.) DMSO (1 mL) 60 °C 18 h 66
20 3 equiv. Cs2CO3 (5 equiv.) DMSO (1 mL) 100 °C 18 h 69
21 3 equiv. Cs2CO3 (5 equiv.) DMSO (2 mL) 80 °C 18 h 81 (86) c
22 3 equiv. Cs2CO3 (3 equiv.) DMSO (2 mL) 80 °C 18 h 78
23 3 equiv. Cs2CO3 (7 equiv.) DMSO (2 mL) 80 °C 18 h 81
24 3 equiv. Cs2CO3 (5 equiv.) DMSO (2 mL) 80 °C 12 h 80
25 3 equiv. Cs2CO3 (5 equiv.) DMSO (2 mL) 80 °C 24 h 82
26 2 equiv. Cs2CO3 (5 equiv.) DMSO (2 mL) 80 °C 18 h 69
27 4 equiv. Cs2CO3 (5 equiv.) DMSO (2 mL) 80 °C 18 h 79
28 3 equiv. Cs2CO3 (5 equiv.) DMSO (4 mL) 80 °C 18 h 86
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a Unless otherwise specified, the reactions were conducted at 80 °C for 18 h by employing 1a (0.5 mmol, 1 equiv.), 2a (3 equiv.), and base (5 equiv.) in solvent (1 mL). b NMR yield determined by employing 4-methoxyanisole as internal standard. c Isolated yield.

Under the above established reaction conditions, we investigated an array of aryl sulfonium salts for this hydroxylation reaction by utilizing acetohydroxamic acid 2a as the hydroxylating agent. As summarized in Table 2, aryl sulfonium salts 1a–k, containing an electron-withdrawing group in the aryl ring, efficiently took part in the hydroxylation to give the corresponding phenols at moderate-to-high yields. More significantly, important functional groups, including cyano, nitro, sulfonyl, formyl, keto, and ester, could be well compatible with the established conditions, which could be retained for downstream derivatization. However, when (4-chlorophenyl)dimethylsulfonium triflate containing a chloro atom in the phenyl ring was used as a substrate, no desired hydroxylative product was obtained, presumably because of its relatively low reactivity as compared with aryl sulfonium salt bearing an electron-withdrawing group in the phenyl ring. In addition, and analogous to a previous report of Fier and Maloney in which the hydroxylation only worked with an electron-poor aryl halide [38], the present reaction also could not be applied to less reactive aryl sulfonium salts derived from an electron-rich aryl ring which bears an electron-donating substituent.

Table 2.

Substrate scope of aryl sulfonium salt a.

graphic file with name molecules-29-00831-i002.jpg
Entry Product Yield (%) b
1 graphic file with name molecules-29-00831-i003.jpg 3a 86
2 graphic file with name molecules-29-00831-i004.jpg 3b 49
3 graphic file with name molecules-29-00831-i005.jpg 3c 95
4 graphic file with name molecules-29-00831-i006.jpg 3d 79
5 graphic file with name molecules-29-00831-i007.jpg 3e 81
6 graphic file with name molecules-29-00831-i008.jpg 3f 61
7 graphic file with name molecules-29-00831-i009.jpg 3g 56
8 graphic file with name molecules-29-00831-i010.jpg 3h 73
9 graphic file with name molecules-29-00831-i011.jpg 3i 51
10 graphic file with name molecules-29-00831-i012.jpg 3j 54
11 graphic file with name molecules-29-00831-i013.jpg 3k 70
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a The reactions were conducted at 80 °C for 18 h by employing aryl sulfonium salt 1a–k (0.5 mmol), acetohydroxamic acid 2a (1.5 mmol), and Cs2CO3 (2.5 mmol) in DMSO (2 mL). b Isolated yield.

In addition to acetohydroxamic acid 2a, we also investigated the hydroxylation of aryl sulfonium salt 1a by employing benzaldoxime [34,35,36,37,39] (1.3 equiv.) as a hydroxylative reagent. In the beginning, we also optimized the reaction conditions. As outlined in Table 3, the reaction of aryl sulfonium salt 1a with benzaldehyde oxime (2b) proceeded smoothly in the presence of Cs2CO3 in DMSO at 80 °C for 4 h to give the hydroxylated product 3a in 58% NMR yield (entry 1). Ensuing screening of reaction solvent (entries 2–7) revealed that DMF served as the more appropriate solvent of the reaction, which slightly improved the reaction efficiency and gave rise to the corresponding product 3a in 67% NMR yield (entry 7). Next, a variety of bases were also examined in the hydroxylating reaction (entries 8–19). However, Cs2CO3 was still the optimal base for the transformation. Pleasingly, by increasing the amount of 2b to 1.5 equivalents, NMR yield of the product could be increased to 74% (entry 20).

Table 3.

Optimization of reaction conditions a.

graphic file with name molecules-29-00831-i014.jpg
Entry Base Solvent Yield (%) b
1 Cs2CO3 DMSO 58
2 Cs2CO3 NMP 63
3 Cs2CO3 MeCN 62
4 Cs2CO3 1,4-dioxane 54
5 Cs2CO3 toluene 15
6 Cs2CO3 THF 56
7 Cs2CO3 DMF 67
8 DBU DMF 16
9 DABCO DMF <5
10 DIPEA DMF <5
11 CsF DMF 57
12 NaOAc DMF <5
13 K3PO4 DMF 56
14 NaHCO3 DMF <5
15 KHCO3 DMF 22
16 Na2CO3 DMF <5
17 K2CO3 DMF 47
18 tBuOK DMF 66
19 LDA DMF 58
20 Cs2CO3 DMF 74 c (70) d
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a Unless otherwise specified, the reactions were conducted at 80 °C for 4 h by employing 1a (0.5 mmol, 1 equiv.), 2b (1.3 equiv.), and base (5 equiv.) in solvent (2 mL). b NMR yield determined by employing 4-methoxyanisole as internal standard. c Using 1.5 equiv. of 2b. d Isolated yield.

Apart from benzaldehyde oxime (2b), a variety of oximes 2 were also evaluated as hydroxide surrogates (Table 4). Of the various oximes 2b–g studied, oxime 2g, derived from pyrrole [39], was found to be the most suitable hydroxylating reagent for the reaction, affording the expected product 3a in 89% NMR yield.

Table 4.

Screening of various oximes a.

graphic file with name molecules-29-00831-i015.jpg
Entry Oxime Yield (%) b
1 graphic file with name molecules-29-00831-i016.jpg 2b 74
2 graphic file with name molecules-29-00831-i017.jpg 2c 41
3 graphic file with name molecules-29-00831-i018.jpg 2d 82
4 graphic file with name molecules-29-00831-i019.jpg 2e 45
5 graphic file with name molecules-29-00831-i020.jpg 2f 38
6 graphic file with name molecules-29-00831-i021.jpg 2g 89 (87) c
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a The reactions were conducted at 80 °C for 4 h by employing 1a (0.5 mmol, 1 equiv.), 2b–g (1.5 equiv.), and Cs2CO3 (5 equiv.) in DMF (2 mL). b NMR yield determined by employing 4-methoxyanisole as internal standard. c Isolated yield.

With the establishment of the optimized reaction conditions, substrate scope of aryl sulfonium salts 1 was investigated with the use of oxime 2g as the hydroxylating agent. As listed in Table 5, a variety of aryl sulfonium salts 1a–k possessing an electron-poor phenyl ring could be amenable to the reaction, leading to the corresponding hydroxylated arenes in 47–95% yields. Analogously, the reactions proceeded with tolerances to a plethora of important functionalities, such as CN, NO2, SO2Me, CHO, COR, and COOR. Additionally, aryl sulfonium salts containing electron-donating group in the aryl ring were proven to be inappropriate for the current hydroxylation reaction, which is similar to reports in the literature [38,39,49,50].

Table 5.

Substrate scope of aryl sulfonium salt a.

graphic file with name molecules-29-00831-i022.jpg
Entry Product Yield (%) b
1 graphic file with name molecules-29-00831-i023.jpg 3a 87
2 graphic file with name molecules-29-00831-i024.jpg 3b 59
3 graphic file with name molecules-29-00831-i025.jpg 3c 95
4 graphic file with name molecules-29-00831-i026.jpg 3d 55
5 graphic file with name molecules-29-00831-i027.jpg 3e 79
6 graphic file with name molecules-29-00831-i028.jpg 3f 52
7 graphic file with name molecules-29-00831-i029.jpg 3g 53
8 graphic file with name molecules-29-00831-i030.jpg 3h 68
9 graphic file with name molecules-29-00831-i031.jpg 3i 60
10 graphic file with name molecules-29-00831-i032.jpg 3j 47
11 graphic file with name molecules-29-00831-i033.jpg 3k 60
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a The reactions were conducted at 80 °C for 4 h by employing aryl sulfonium salt 1a–k (0.5 mmol), 2g (0.75 mmol), and Cs2CO3 (2.5 mmol) in DMF (2 mL). b Isolated yield.

Finally, the scalability of the reactions was also investigated. As illustrated in Scheme 2, 3 mmol scale reaction of aryl sulfonium salt 1a with both 2a and 2g worked equally well under the optimized reaction conditions, producing the anticipated product 3a in 73% and 75% yields, respectively.

Scheme 2.

Scheme 2

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Scale-up synthesis.

Based on previous reports [34,38,50], possible mechanisms for these two hydroxylative reactions have been tentatively proposed. As shown in Figure 1a, for the reaction of aryl sulfonium salt with aldehyde oxime, the reaction possibly proceeds via the nucleophilic substitution of the aldehyde oxime with the sulfonium salt under the action of base to give intermediate A, accompanied by the generation of dimethyl sulfide as a byproduct. Next, a base-mediated deprotonation of intermediate A, followed by fragmentation and subsequent protonation, affords the corresponding phenol as the final product and aryl nitrile as a byproduct. With regard to hydroxylation employing acetohydroxamic acid as hydroxide source (Figure 1b), the reaction presumably occurs through a similar base-facilitated nucleophilic substitution of acetohydroxamic acid with aryl sulfonium salt to produce intermediate B, along with the formation of Me2S as a byproduct. Subsequently, a Lossen rearrangement takes place to yield the desired phenol after acidific workup.

Figure 1.

Figure 1

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Tentatively proposed mechanisms. (a) When using aldehyde oxime as hydroxylative source; (b) When using acetohydroxamic acid as hydroxylative source.

3. Materials and Methods

3.1. General Information

Unless otherwise specified, the reagents were purchased from commercial suppliers and used without further purification. All reactions were conducted under N2 atmosphere using undistilled solvent. Analytical thin layer chromatography (TLC) was performed using silica gel plate (0.2 mm thickness). Subsequent to elution, plates were visualized using UV radiation (254 nm). Flash chromatography was performed using Merck silica gel (200–300 mesh) for column chromatography with freshly distilled solvents. IR spectra were recorded on an FT-IR spectrophotometer using KBr optics. 1H and 13C NMR spectra were recorded in CDCl3 and DMSO-d6 on Bruker Avance or Jeol 400 MHz spectrometers. The chemical shifts (δ) are reported in ppm and coupling constants (J) in Hz. NMR splitting patterns are designated as singlet (s), doublet (d), triplet (t), quartet (q), multiplet (m), doublet of doublets (dd), doublet of triplets (dt), doublet of quartets (dq), triplet of doublets (td), triplet of triplets (tt), quartet of doublets (qd), doublet of doublet of doublets (ddd), etc. Tetramethylsilane (TMS) served as internal standard for 1H and 13C NMR analysis. High resolution mass spectra (HRMS) were obtained via a Waters Q-TOF Premier Spectrometer (ESI source).

3.2. Experimental

3.2.1. General Procedure for the Synthesis of Aryl Sulfonium Salts 1a–k

A 50 mL single-neck round-bottom flask was sequentially charged with aryl thioether (20 mmol, 1.0 equiv.), DCE (20 mL), and MeOTf (3938.4 mg, 24 mmol, 1.2 equiv.). The reaction mixture was vigorously stirred at room temperature for 12 h. Then, solvent was evaporated and the residual was purified through silica gel column chromatography using petroleum ether and EtOAc as eluent to afford the analytically pure product of aryl sulfonium salts 1a–k. Spectral data of these compounds are in accordance with those previously documented [62,63,64,65].

3.2.2. General Procedure for the Synthesis of Oximes 2b–g

A 250 mL round-bottom flask was sequentially charged with aryl aldehyde (20.0 mmol, 1 equiv.), MeOH (100 mL), Na2CO3 (2.54 g, 24 mmol, 1.2 equiv.), and NH2OH∙HCl (1.67 g, 24 mmol, 1.2 equiv.). The reaction mixture was then heated to reflux and stirred for 2 h. The reaction was allowed to cool to room temperature and MeOH was removed under reduced pressure. The residue was dissolved in EtOAc (50 mL) and H2O (50 mL). The organic phase was separated and the aqueous phase was extracted with EtOAc (50 mL × 2). The organic extracts were combined, washed with brine (50 mL), and dried over Na2SO4. The extracts were concentrated under reduced pressure to afford the crude product, which was purified via silica gel column chromatography (using EtOAc/petroleum ether + 3% Et3N as eluents) to afford the analytically pure oximes 2b–g. Spectral data of the products are in accordance with those previously documented [39].

3.2.3. General Procedure for the Reaction of Aryl Sulfonium Salt with Acetohydroxamic Acid

To an oven-dried Schlenk tube equipped with a magnetic stir bar was sequentially added aryl sulfonium salt 1 (0.5 mmol, 1 equiv.), acetohydroxamic acid 2a (112.6 mg, 1.5 mmol, 3 equiv.), and Cs2CO3 (814.6 mg, 2.5 mmol, 5 equiv.). Then, dry DMSO (2 mL) was added into the tube by syringe. The reaction mixture was stirred at 80 °C for 18 h before quenching with aqueous hydrochloric acid (6 mmol, 6 mL, 1 M in water) and extracting with EtOAc (20 mL × 3). The organic layers were combined, washed with brine, and dried over Na2SO4. The extracts were concentrated under reduced pressure to afford the crude product, which was further purified via silica gel column chromatography (using EtOAc/petroleum ether as eluents) to yield the analytically pure product 3.

3.2.4. General Procedure for the Reaction of Aryl Sulfonium Salt with Oxime

To an oven-dried Schlenk tube equipped with a magnetic stir bar was sequentially added aryl sulfonium salt 1 (0.5 mmol, 1 equiv.), oxime 2g (93.1 mg, 0.75 mmol, 1.5 equiv.), and Cs2CO3 (814.6 mg, 2.5 mmol, 5 equiv.). Then dry DMF (2 mL) was added into the tube by syringe. The reaction mixture was stirred at 80 °C for 4 h before quenching with aqueous hydrochloric acid (6 mmol, 6 mL, 1 M in water) and extracting with EtOAc (20 mL × 3). The organic layers were combined, washed with brine, and dried over Na2SO4. The extracts were concentrated under reduced pressure to afford the crude product, which was further purified through silica gel column chromatography (using EtOAc/petroleum ether as eluents) to yield the analytically pure product 3.

3.2.5. Scale-Up Reaction of Sulfonium Salt 1a with Acetohydroxamic Acid 2a

To an oven-dried Schlenk tube equipped with a magnetic stir bar was sequentially added aryl sulfonium salt 1a (940.0 mg, 3 mmol, 1 equiv.), acetohydroxamic acid 2a (1013.4 mg, 9 mmol, 3 equiv.), and Cs2CO3 (7331.4 mg, 15 mmol, 5 equiv.). Then dry DMSO (12 mL) was added into the tube by syringe. The reaction mixture was stirred at 80 °C for 18 h before quenching with aqueous hydrochloric acid (36 mmol, 36 mL, 1 M in water) and extracting with EtOAc (80 mL × 3). The organic layers were combined, washed with brine, and dried over Na2SO4. The extracts were concentrated under reduced pressure to afford the crude product, which was further purified through silica gel column chromatography (using EtOAc/petroleum ether as eluents) to yield the analytically pure product 3a in 73% yield (262.9 mg).

3.2.6. Scale-Up Reaction of Sulfonium Salt 1a with Oxime 2g

To an oven-dried Schlenk tube equipped with a magnetic stir bar was sequentially added aryl sulfonium salt 1a (940.0 mg, 3 mmol, 1 equiv.), oxime 2g (419.0 mg, 4.5 mmol, 1.5 equiv.), and Cs2CO3 (7331.4 mg, 15 mmol, 5 equiv.). Then, dry DMSO (12 mL) was added into the tube by syringe. The reaction mixture was stirred at 80 °C for 4 h before quenching with aqueous hydrochloric acid (36 mmol, 36 mL, 1 M in water) and extracting with EtOAc (80 mL × 3). The organic layers were combined, washed with brine, and dried over Na2SO4. The extracts were concentrated under reduced pressure to afford the crude product, which was further purified through silica gel column chromatography (using EtOAc/petroleum ether as eluents) to yield the analytically pure product 3a in 75% yield (270.1 mg).

4-Hydroxybenzonitrile (3a). Purification of this product was performed via silica gel column chromatography employing petroleum ether and ethyl acetate as eluant (petroleum ether/EtOAc = 15:1) with a yield = 86%, 51.4 mg using 2a as hydroxylating agent and a yield = 87%, 51.8 mg using 2g as hydroxylating agent. White solid. 1H NMR (400 MHz, CDCl3): δ 7.57–7.51 (m, 2H), 7.18 (brs, 1H), 6.97–6.90 (m, 2H) ppm. 13C NMR (100 MHz, CDCl3): δ 160.4, 134.3, 119.3, 116.5, 102.6 ppm. IR (KBr, neat): ν = 3292, 2927, 2856, 1610, 1586, 1508, 1286, 1166, 835, 700, 458 cm−1. HRMS (ESI, m/z): calculated for C7H6NO [M + H]+ 120.0444, found: 120.0442. Spectral data of the product are in accordance with previously documented data [85].

4-Hydroxy-2-methylbenzonitrile (3b). Purification of this product was performed via silica gel column chromatography employing petroleum ether and ethyl acetate as eluant (petroleum ether/EtOAc = 20:1) with a yield = 49%, 32.9 mg using 2a as hydroxylating agent and a yield = 59%, 39.5 mg using 2g as hydroxylating agent. Yellow solid. 1H NMR (400 MHz, CDCl3): δ 7.48 (d, J = 8.4 Hz, 1H), 6.78 (d, J = 2.5 Hz, 1H), 6.74 (dd, J = 8.4, 2.5 Hz, 1H), 6.47 (brs, 1H), 2.48 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ 159.9, 144.5, 134.5, 118.6, 117.2, 113.8, 103.8, 20.5 ppm. IR (KBr, neat): ν = 3300, 2921, 2225, 1616, 1576, 1498, 1303, 1231, 1163, 1098 cm−1. HRMS (ESI, m/z): calculated for C8H8KNO [M+K]+ 172.0159, found: 172.0170. Spectral data of the product are in accordance with previously documented data [24].

4-Nitrophenol (3c). Purification of this product was performed via silica gel column chromatography employing petroleum ether and ethyl acetate as eluant (petroleum ether/EtOAc = 20:1) with a yield = 95%, 66.3 mg using 2a as hydroxylating agent and a yield = 95%, 66.1 mg using 2g as hydroxylating agent. Yellow solid. 1H NMR (400 MHz, CDCl3): δ 8.21–8.13 (m, 2H), 6.98–6.91 (m, 2H), 6.64 (brs, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ 161.7, 141.4, 126.3, 115.8 ppm. IR (KBr, neat): ν = 3337, 2962, 2360, 2342, 1592, 1498, 1339, 1289, 1262, 1112 cm−1. HRMS (ESI, m/z): calculated for C6H6NO3 [M + H]+ 140.0342, found: 140.0353. Spectral data of the product are in accordance with previously documented data [85].

3-Methyl-4-nitrophenol (3d). Purification of this product was performed via silica gel column chromatography employing petroleum ether and ethyl acetate as eluant (petroleum ether/EtOAc = 20:1) with a yield = 79%, 60.5 mg using 2a as hydroxylating agent and a yield = 55%, 42.4 mg using 2g as hydroxylating agent. White solid. 1H NMR (400 MHz, DMSO-d6): δ 10.79 (brs, 1H), 8.00–7.95 (m, 1H), 6.79–6.74 (m, 2H), 2.49 (s, 3H) ppm. 13C NMR (100 MHz, DMSO-d6): δ 162.7, 140.9, 137.3, 128.3, 119.2, 114.3, 21.5 ppm. IR (KBr, neat): ν = 3301, 3090, 2929, 1589, 1507, 1477, 1458, 1317, 1260, 1077 cm−1. HRMS (ESI, m/z): calculated for C7H8NO3 [M + H]+ 154.0499, found: 154.0498. Spectral data of the product are in accordance with previously documented data [86].

4-(Methylsulfonyl)phenol (3e). Purification of this product was performed via silica gel column chromatography employing petroleum ether and ethyl acetate as eluant (petroleum ether/EtOAc = 5:1) with a yield = 81%, 70.1 mg using 2a as hydroxylating agent and a yield = 79%, 68.3 mg using 2g as hydroxylating agent. Yellow solid. 1H NMR (400 MHz, CDCl3): δ 7.78–7.65 (m, 3H), 7.00–6.92 (m, 2H), 3.06 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ 161.4, 130.6, 129.6, 116.2, 44.9 ppm. IR (KBr, neat): ν = 3375, 3017, 2918, 1588, 1502, 1447, 1302, 1283, 1144, 1090 cm−1. HRMS (ESI, m/z): calculated for C7H9O3S [M + H]+ 173.0267, found: 173.0266. Spectral data of the product are in accordance with previously documented data [24].

4-Hydroxybenzaldehyde (3f). Purification of this product was performed via silica gel column chromatography employing petroleum ether and ethyl acetate as eluant (petroleum ether/EtOAc = 20:1) with a yield = 61%, 37.3 mg using 2a as hydroxylating agent and a yield = 52%, 31.8 mg using 2g as hydroxylating agent. White solid. 1H NMR (400 MHz, CDCl3): δ 9.84 (s, 1H), 7.86–7.78 (m, 2H), 7.38 (brs, 1H), 7.04–6.97 (m, 2H) ppm. 13C NMR (100 MHz, CDCl3): δ 191.9, 162.4, 132.8, 129.3, 116.1 ppm. IR (KBr, neat): ν = 3167, 2878, 1668, 1599, 1453, 1316, 1287, 1218, 1161, 834 cm−1. HRMS (ESI, m/z): calculated for C7H7O2 [M + H]+ 123.0441, found: 123.0453. Spectral data of the product are in accordance with previously documented data [87].

(4-Hydroxyphenyl)(phenyl)methanone (3g). Purification of this product was performed via silica gel column chromatography employing petroleum ether and ethyl acetate as eluant (petroleum ether/EtOAc = 20:1) with a yield = 56%, 55.9 mg using 2a as hydroxylating agent) and a yield = 53%, 52.8 mg using 2g as hydroxylating agent. Yellow solid. 1H NMR (400 MHz, CDCl3): δ 7.82–7.73 (m, 4H), 7.65 (brs, 1H), 7.61–7.55 (m, 1H), 7.52–7.44 (m, 2H), 6.99–6.91 (m, 2H) ppm. 13C NMR (100 MHz, CDCl3): δ 196.8, 160.8, 138.0, 133.1, 132.2, 129.8, 129.5, 128.3, 115.4 ppm. IR (KBr, neat): ν = 3150, 2346, 1634, 1602, 1559, 1507, 1313, 1288, 1232, 1148 cm−1. HRMS (ESI, m/z): calculated for C13H11O2 [M + H]+ 199.0754, found: 199.0765. Spectral data of the product are in accordance with previously documented data [24].

2-Hydroxyanthracene-9,10-dione (3h). Purification of this product was performed via silica gel column chromatography employing petroleum ether and ethyl acetate as eluant (petroleum ether/EtOAc = 20:1) with a yield = 73%, 81.8 mg using 2a as hydroxylating agent and a yield = 68%, 76.5 mg using 2g as hydroxylating agent. Yellow solid. 1H NMR (400 MHz, CDCl3): δ 8.17–8.14 (m, 2H), 8.08 (d, J = 8.5 Hz, 1H), 7.93–7.85 (m, 2H), 7.49 (d, J = 2.5 Hz, 1H), 7.24 (dd, J = 8.5, 2.6 Hz, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ 183.0, 181.5, 163.6, 135.6, 134.9, 134.4, 133.6, 133.5, 130.3, 127.03, 127.01, 125.6, 122.0, 112.7 ppm. IR (KBr, neat): ν = 3357, 2960, 2255, 1671, 1581, 1450, 1342, 1304, 1022, 997 cm−1. HRMS (ESI, m/z): calculated for C14H9O3 [M + H]+ 225.0546, found: 225.0551. Spectral data of the product are in accordance with previously documented data [88].

1-(4-Hydroxyphenyl)ethan-1-one (3i). Purification of this product was performed via silica gel column chromatography employing petroleum ether and ethyl acetate as eluant (petroleum ether/EtOAc = 20:1) with a yield = 51%, 34.7 mg using 2a as hydroxylating agent and a yield = 60%, 41.0 mg using 2g as hydroxylating agent. White solid. 1H NMR (400 MHz, CDCl3): δ 8.15 (brs, 1H), 7.95–7.88 (m, 2H), 6.97–6.92 (m, 2H), 2.58 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ 199.0, 161.7, 131.3, 129.3, 115.6, 26.3 ppm. IR (KBr, neat): ν = 3306, 2995, 2926, 1663, 1603, 1577, 1512, 1357, 1279, 1219, 1166 cm−1. HRMS (ESI, m/z): calculated for C8H9O2 [M + H]+ 137.0597, found: 137.0594. Spectral data of the product are in accordance with previously documented data [85].

Methyl 4-hydroxybenzoate (3j). Purification of this product was performed via silica gel column chromatography employing petroleum ether and ethyl acetate as eluant (petroleum ether/EtOAc = 20:1) with a yield = 54%, 41.1 mg using 2a as hydroxylating agent and a yield = 47%, 35.8 mg using 2g as hydroxylating agent. White solid. 1H NMR (400 MHz, CDCl3): δ 7.97–7.91 (m, 2H), 7.15 (brs, 1H), 6.93–6.87 (m, 2H), 3.90 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3): δ 167.8, 160.6, 132.0, 121.9, 115.3, 52.2 ppm. IR (KBr, neat): ν = 3307, 2962, 1683, 1607, 1588, 1515, 1435, 1278, 1163, 1106 cm−1. HRMS (ESI, m/z): calculated for C8H9O3 [M + H]+ 153.0546, found: 153.0549. Spectral data of the product are in accordance with previously documented data [85].

5-Hydroxyisobenzofuran-1(3H)-one (3k). Purification of this product was performed via silica gel column chromatography employing petroleum ether and ethyl acetate as eluant (petroleum ether/EtOAc = 20:1) with a yield = 70%, 52.8 mg using 2a as hydroxylating agent and a yield = 60%, 45.1 mg using 2g as hydroxylating agent. Yellow solid. 1H NMR (400 MHz, DMSO-d6): δ 10.67 (brs, 1H), 7.70–7.60 (m, 1H), 6.98–6.89 (m, 2H), 5.26 (s, 2H) ppm. 13C NMR (100 MHz, DMSO-d6): δ 171.0, 163.6, 150.8, 127.2, 117.6, 116.1, 108.9, 69.6 ppm. IR (KBr, neat): ν = 3270, 2962, 2925, 1718, 1603, 1467, 1434, 1346, 1273, 1097 cm−1. HRMS (ESI, m/z): calculated for C8H7O3 [M + H]+ 151.0390, found: 151.0399. Spectral data of the product are in accordance with previously documented data [32].

4. Conclusions

In conclusion, the hydroxylation of aryl sulfonium salts by utilizing acetohydroxamic acid and oxime as hydroxylating reagents was developed. The reactions proceeded effectively with the aid of cesium carbonate to afford a series of hydroxylated arenes in moderate-to-high yields with broad functional group compatibility. In addition, the hydroxylation could be subjected to scale-up synthesis, leading to the desired phenol in a good yield.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/molecules29040831/s1.

molecules-29-00831-s001.zip (1MB, zip)

Author Contributions

Synthesis and characterization, X.-B.H., Q.-Q.F. and X.-Y.H.; methodology and project administration, X.-Q.C.; writing—original draft preparation, and supervision, Z.-L.S.; writing—review and editing, and funding acquisition, Z.-L.S., C.M. and W.C. All authors have read and agreed to the published version of the manuscript.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data are contained within the article and Supplementary Materials.

Conflicts of Interest

The authors declare no conflicts of interest.

Funding Statement

We gratefully acknowledge the financial support from Nanjing Tech University (Start-up Grant No. 39837118), Jiaxing University, and Soochow University.

Footnotes

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

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