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Controllable Sulfoxidation and Sulfenylation with Organic Thiosulfate Salts via Dual Electron- and Energy-Transfer Photocatalysis Yiming Li, Ming Wang, and Xuefeng Jiang ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b02735 • Publication Date (Web): 03 Oct 2017 Downloaded from http://pubs.acs.org on October 4, 2017
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ACS Catalysis
Controllable Sulfoxidation and Sulfenylation with Organic Thiosulfate Salts via Dual Electron- and Energy-Transfer Photocatalysis Yiming Li † ‡, Ming Wang † ‡, Xuefeng Jiang *,†,§, # †
Shanghai Key Laboratory of Green Chemistry and Chemical Process, East China Normal University, 3663 North Zhongshan Rd., Shanghai 200062, P. R. China. §State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300071, P. R. China. #State Key Laboratory of Organometallic Chemistry, Shanghai, Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China. ABSTRACT: Sulfoxides and sulfides are two important functional groups in organic molecules, containing different valence states of sulfur. Both sulfoxidation and sulfenylation with common sulfurating reagents were successfully tuned via a facile variation of the atmosphere under photocatalyzed conditions. The sulfoxidation and sulfenylation transformations involved tandem electron/energy-transfer and single electron-transfer processes, respectively. Late-stage sulfoxidation for pharmaceuticals and sugar derivatives was established to be highly compatible. Divergent formal syntheses of sulfoxide/sulfide-containing marketed pharmaceuticals were switchably implemented. Gram-scale operations further demonstrated the practicability of the protocol.
KEYWORDS. Sulfoxidation, Sulfenylation, Electron Transfer, Energy Transfer, Photocatalysis Various organosulfur molecules widely exist in nature.1 In addition, synthetic sulfur-containing compounds are also abundant with miscellaneous functions especially for pharmaceuticals.2 Sulfide and sulfoxide are usually studied with each other in drug discovery, due to their mutual transformations assisted by enzymes in vivo.3 Similar molecular backbones with different oxidation states of sulfur in pharmaceuticals have afforded a diversity of drug activities (Scheme 1a). Sulfide-containing albendazole,4 an oral medication for the treatment of intestinal parasites in humans, is a vital drug on the list of essential medicines from the World Health Organization (WHO).5 The corresponding sulfoxide-containing ricobendazole is commonly applied as an antihelminthic agent against lungworms and roundworms in ruminants.6 Sulfidecontaining arbidol (umifenovir) is an antiviral pharmaceutical for prophylaxis and treatment of infections with influenza A and B viruses in Russia and China,7 while its sulfoxide derivative ARB-IIIf has been found to be an exclusive inhibitor of chikungunya virus (a mosquito-borne arthrogenic alphavirus).8 Sulfide-containing sulprofos is applied to control worms on cotton and tobacco,9 while the similar sulfoxidecontaining fensulfothion10 is an insecticide for corn and sugar cane. Considering the accompanying and complementary characteristics between sulfides11 and sulfoxides,12,13 a divergent construction strategy with a common precursor is in urgent demand. However, contradictions11,14 between sulfenylation and oxygenation in transition-metal-catalyzed coupling have brought challenges toward this goal. A mild photocatalyzed15 system with different kinds of catalytic modes (single electron transfer and energy transfer)16 provides an opportunity for both sulfenylation17 and oxygenation,18 despite the poor compatibility among the sulfur species, aryl radical, and active oxygen (Scheme 1b). Our masked strategy,19 in which stabilization of a sulfur radical was realized through an electronic conjugation and steric hindrance effect, could impede the
highly active undesired processes, such as homocoupling and over oxidation. (Scheme 1c). Scheme 1. Selective Sulfoxidation and Sulfenylation. a) Sulfide and Sulfoxide: Br O n
Pr
S
S Me S OH SnPr Me P O N OEt CO2Et Me Arbidol Sulprofos and B Worms on Cotton and Tobacco Influenza A Me
OMe
N
N
NH
S
N H Albendazole Intestinal Parasites in Human
O n
Pr
O
S
CF3 O S
OMe
N
NH N H Ricobendazole Lungworms in Ruminants
OH
Me
O
N Me CO2
S
S OEt P OEt
O
tBu
ARB-IIIf Chikungunya Virus
Fensulfothion Insects on Corn and Sugar Cane
b) Our Concept: Ar
S
+
Ar
R
+
R S
[O] Ar
O S
R
Challenges
Ar
Ar
R
S
S
R
Ar
OH
c) This Work: Ar
S
EY, hv Ar/Alkyl
N2
S Ar2IBF4 + Ar/Alkyl Mask Mask = SO3Na
EY, hv Air
Ar
O S
Ar/Alkyl
We commenced this study using n-pentyl thiosulfate salt and diphenyl iodonium in air under photocatalyzed conditions. Unfortunately, no sulfoxide was detected when catalyzed by tris(bipyridine)ruthenium(II) chloride with potassium carbonate in a mixture of dimethyl sulfoxide and water.19f When subjected to the dye eosin Y (EY) in methanol, pentyl(phenyl)sulfoxide 3a was delightedly obtained in 20% yield (Table 1, entry 1). Other solvents, such as dimethyl sulfoxide,
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N,N-dimethylformamide, and water, did not deliver 3a (Table 1, entries 2-4). Different bases were also checked (Table 1, entries 5-7), in which Hünig’s base, diisopropylethylamine, improved the yield to 31%. Zinc acetate, which is known to improve the selectivity during oxidation,20 elevated the yield to 53% (Table 1, entry 8). Other Lewis acids and Brønsted acids did not elevate the efficiency (Table 1, entries 9 and 10). A higher concentration afforded a better result with 65% yield (Table 1, entry 11). The solvent combination of methanol and acetonitrile, adjusting the solubility of starting materials, yielded 77% sulfoxide (Table 1, entry 12). A green LED (λ = 530 nm), which matches the maximum absorption wavelength of eosin Y (520 nm), afforded 3a in 82% isolated yield (Table 1, entry 13). Conveniently, by only altering the atmosphere to nitrogen, pentyl(phenyl)sulfane 4a was efficiently obtained in 84% isolated yield (Table 1, entries 14 and 15). Table 1. Selectivity Establishmenta O Ph
S
BF4 I Sulfidation Ph 1a + NaO3S2 nPent 2a
Sulfoxidation n
Pent
3a
entry
base
additive
1
K2CO3
-
2
K2CO3
-
3
K2CO3
-
4
K2CO3
-
5
KOH
6
KOtBu
7
DIPEA
8
DIPEA
Ph
Zn(OAc)2 .
Ph
solvent
yield/3a
MeOH
20
DMSO
trace
DMF
trace
H 2O
trace
MeOH
15
MeOH
12
MeOH
31
MeOH
53
DIPEA
BF3 OEt2
MeOH
30
10
DIPEA
HOAc
MeOH
22
11
DIPEA
Zn(OAc)2
MeOHc
65
12
DIPEA
Zn(OAc)2
MeOH/MeCNd
77
13
DIPEA
Zn(OAc)2
MeOHd
85(82)
14g
DIPEA
Zn(OAc)2
MeOHd
DIPEA
.
Zn(OAc)2 2H2
Of
MeOH
c
n
Pent
4a
9
15g
S
-
b
yield/4a
b
-
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ides (3j and 3k) were also achieved. Various thiosulfate salts substituted with benzyl (3l), ether (3m and 3n), cyano (3o), and ester (3p) groups were successfully converted. It is noteworthy that a functional group with an active hydrogen hydroxyl (3q) was well retained. In addition to aryl alkyl sulfoxides, diaryl ones were delightedly afforded, which can be hardly achieved under mild visible-light-promoted oxygenation of sulfides.12c,18 Electron-neutral 3r and 3s were acquired in good yields. Chloro and bromo substituents were compatible (3s-3u). Sulfoxide 3u was further confirmed by X-ray diffraction.21 Impressively, diarylsulfoxides with electrondeficient groups, such as fluoro (3v) and ester (3w) groups, were also synthesized. Late-stage sulfoxidation of the functional molecules furanose (3x) and pyranose (3y) were implemented from side-chain-derivatised thiosulfates. Moreover, nitro-containing metronidazole was sulfoxidized in 50% yield (3z). On the other hand, aryl alkyl sulfides were obtained in good to excellent yields with a variety of functional substituents, such as bromo (4b), hydroxyl (4d), nitrile (4e), benzyl (4f and 4g), and propargyl (4h) groups. Particularly, this method showed great potential for constructing diaryl sulfides, wherein the electronic effects of substituents on both the diaryl iodonium salts and thiosulfate salts did not affect the efficiency (4i-4s). The steric effects were illuminated through the synthesis of 2-methyl- and 2,4,6-trimethyl-substituted sulfides 4m and 4n. Gram-scale operation further demonstrated the utility, in which 3a and 4i were synthesized on a 10 mmol scale under these mild and easily handled conditions. With these tunable systems in hand, the controllable formal synthesis of albendazole,22 ricobendazole,22 ARB-IIIf,8 and fensulfothion23 was conducted, as discussed below (Scheme 2).
e
68 86(84)
a Standard conditions: 1a (0.2 mmol), 2a (0.6 mmol), catalyst (2 mol%), additive (0.4 mmol), base (2 equiv.), and solvent (1.0 mL) were added and stirred for 24 h under the irradiation of a 23 W CFL. b1H NMR yields (%). Isolated yields (%) are in parentheses. c0.5 mL. d0.3/0.1 mL. e18 W green LED. f10 mol%. gNitrogen atmosphere was applied instead of air.
With this tunable protocol in hand, the sulfoxide library was first established (Table 2). Diaryliodonium salts with electrondonating (3b) and electron-withdrawing groups in different positions (3c and 3g) delivered the corresponding sulfoxides smoothly. Fluoro, chloro, and bromo substituents were well tolerated (3d-f), which could be further modified with cross coupling reactions. Sterically hindered substrates with 2methyl and 2,4,6-trimethyl groups still efficiently underwent the reaction (3h and 3i). Fused- and hetero-aromatic sulfox-
Further control experiments were pursued to gain insight into the mechanism. First, UV-Vis absorption experiments showed that only eosin Y possessed obvious absorption in the visible-light region (SI, Figure S1). Stern–Volmer fluorescent quenching experiments demonstrated that diaryl iodonium, instead of the thiosulfate salt, quenched the excited catalyst EY* efficiently (SI, Figure S2). Moreover, radical quenching experiments with 2,2,6,6-tetramethylpiperidinooxy (TEMPO) completely suppressed both the sulfoxidation and sulfenylation pathways (SI, Tables S1 and S2). The results above indicate that the current reactions started with a single electron transfer between EY* and the aryliodonium salt. Second, a control experiment with sulfide 4a was carried out under standard conditions for sulfoxidation (Table 3, entry 1), providing an almost quantitative transformation to the related sulfoxide 3a, which indicated that the sulfoxidation operated by cascade sulfenylation and oxygenation processes. The fluorescence of Eosin Y was not quenched by a sulfide, which demonstrated that there is no direct interaction of the sulfide with EY* (SI, Figure S2). The oxygen radical anion (O 2 -.) quencher 1,4-benzoquinone (BQ)18d had no effect on the oxygenation reaction (Table 3, entry 2). However, the singlet oxygen (1O 2 ) quencher cobaltic acetylacetonate, [Co(acac) 3 ],18g dramatically decreased the yield with a recovery of 85% sulfide (Table 3, entry 3). Additional fluorescent quenching experiments revealed that neither BQ nor Co(acac) 3 quenched EY* (Figure 1, for details, see Figure S3), which showed that 1 O 2 is the key active oxygen species generated through energy 3 and O2. Over transfer between EY*
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Table 2: Substrate Scopes of Sulfoxidesa and Sulfidesb
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
O Ar
S
Sulfoxidation R
BF4 I Ar 1
Ar
3 O S
S
Pent
R
n
S Pent
tBu
3e 70%
Cl
3h 57%
2-Me
3c 67%
CF3 3f 83%
Br
3i 50%
2,4,6-Me
O
O
S
S
S n
n
Pent
S
Pent
4a 84% R = H
S
Me
OH 6
4c 90%h
4d 50%
Br
4b 87%
3j 81%
R
O CN
S
S
R
R 3l 57% R = Ph 3o 62% R = (CH2)2CN 3r 68%d R = Me 3m 63% CH2OEt 3p 74% (CH2)2CO2Me 3s 65%d Cl O 3n 60% 3q 77% (CH2)5OH
3k 50%
O
Ph
S
S
4f 73% R = H tBu 4g 60%
4e 60%
O
S R
Me S
S
70%d
R = Cl
3u 72%d
Br
3v 62%
Late Stage Sulfoxidation Me Me O O O
3x 84% f,g
Me
OMe
4i 77% R = Hi 4k 84% R = Br F 4l 71% CF3 4j 65%
e
R=F 3w 55%e CO2Et
3u
Me
OMe
R
OMe
4h 46%
Me
S
S R
O
R
Pent
S
O
S 4
2
3g 87% R = 3-CF3
3b 88%
3t
Ar
R
R 3a 82% R = Hc 3d 64% R = F
n
Sulfidation
R S2O3Na
O
O n
+
OMe 4n 42%
4m 68%
Ph O
S Ph O O Me O Me
S
O
3
OBz
O O BzO
Me 3z 50%f
OBzOMe
S
N
O 3y 61%f,g
S
S
NO2
S
N
CF3 4o 73%
R
OMe
OMe 4p 53%
4q 83% R = Me 4r 75% Cl CF3 4s 79%
aStandard
conditions for sulfoxidation: diaryl iodonium salt (0.2 mmol), thiosulfate salt (0.6 mmol), eosin Y (0.004 mmol), DIPEA (0.4 mmol), Zn(OAc) 2 (0.4 mmol), MeOH/MeCN = 0.3/0.1 mL, air, 18 W green LED, 24 h. bStandard conditions for sulfenylation: diaryl iodonium salt (0.2 mmol), thiosulfate salt (0.6 mmol), eosin Y (0.004 mmol), DIPEA (0.4 mmol), Zn(OAc) 2 .2H 2 O (0.02 mmol), MeOH = 0.5 mL, N 2 , 23 W CFL, 24 h. c76%, 10 mmol scale. dAir, 12 h, then O 2 , 24 h. eAir, 12 h, then O 2 , 48 h. f23 W CFL, gCH 3 CN (0.4 mL). hMethyl thiosulfate salt (5 equiv.). i63%, 10 mmol scale.
Scheme 2: Formal Synthesis of Albendazole, Ricobendazole, ARB-IIIf, and Fensulfothiona,b BF4 Ar
I
Ar'
+
1
n
Eosin Y
NaO3S2 R
Pr
N2
2
S
NO2 NHAc
6a 76%[c] Albendazole Eosin Y
n
Pr
NO2
S
NHAc 5a 75%[c] Ricobendazole aStandard
Table 3: Control Experiments
Air
O
8 and EY+. produced the sulfide and regenerated the lowenergy EY. An energy-transfer process was involved between 3 O 2 and EY*, generating 1O 2 . The persulfoxide 9,12c,18b,g which was obtained via the combination of the sulfide and 1O 2 , stabilized by zinc acetate18c and finally delivered the sulfoxide with another sulfide.
CF3 O S
Me
O
CO2Et
N
Me
S
CO2tBu
Ph O OEt P O OEt
S
n
Pent
20 h 4a entry
5c 50%[c]
5b 50% ARB-IIIf
Fensulfothion bStandard
conditions for sulfoxidation. sulfenylation. cAr’ = 2,4,6-trisopropylphenyl.
conditions for
all, a proposed mechanism was depicted, as show in Scheme 3 below: EY* was generated from EY under visible-light irradiation, which subsequently interacted with diaryliodonium salt 1 through a single electron-transfer process. The newly formed aryl radical 7 coupled with the thiosulfate salt to produce sulfide radical 8. The following electron-transfer process between
standard conditions for sulfoxidation
1
O Ph
S
n
Pent
3a alteration of conditions -
yield 99%
2
+ BQ (6 mol%)
97%
3
+ Co(acac)3 (6 mol%)
11% + 85% 4a
In conclusion, a selective construction of organic sulfurs in different valence states from common thiosulfate salts was developed under visible-light-catalyzed conditions via easily tuning the reaction atmosphere. Late-stage sulfoxidation, switchable synthesis of pharmaceuticals, and gram-scale operations were systematically established. Mechanistic studies
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Scholar) at Shanghai Institutions of Higher Learning, and National Program for Support of Top-Notch Young Professionals.
REFERENCES
Figure 1: Stern–Volmer Fluorescent Quenching Experiments Scheme 3: Proposed Mechanism
Ar Ar
S 8
SO3Na
S
O R
Ar
R EY
EY+
ELECTRON TRANSFER
3O
S
Zn(OAc)2 R
2
ENERGY TRANSFER
hv
Ar S
R
OAc O O Zn S OAc Ar R 10 Zn(OAc)2
EY* NaO3S
S
1O
O O S Ar R 9
2
R
2
Ar 7 + ArI + BF4
BF4 I Ar 1 Ar
Ar
S
R
indicated that the sulfoxidation might involve cascade electron- and energy-transfer processes, whereas a single electron transfer might dominate in the sulfenylation pathway. A sulfoxide-containing pharmaceutical library is being constructed in our group.
ASSOCIATED CONTENT Supporting Information. The supporting Information is available free of charge via the Internet at http://pubs.acs.org. Detailed mechanistic studies, experimental procedures, characterization data, X-ray analyses of compound 3u, and NMR spectra for the compounds (PDF).
AUTHOR INFORMATION Corresponding Author *E-mail:
[email protected].
ORCID Xuefeng Jiang: 0000-0002-1849-6572
Author Contributions ‡These authors contributed equally.
ACKNOWLEDGMENT Financial support was provided by NSFC (21672069, 21472050), DFMEC (20130076110023), Fok Ying Tung Education Foundation (141011), the Program for Shanghai Rising Star (15QA1401800), Professor of Special Appointment (Eastern
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(16) Metternich, J. B.; Gilmour, R. J. Am. Chem. Soc. 2016, 138, 1040-1043. (17) a) Wang, X.; Cuny, G. D.; Noúl, T. Angew. Chem. Int. Ed. 2013, 52, 7860-7864. (b) Majek, M.; von Wangelin, A. J. Chem. Commun. 2013, 49, 5507-5510. (18) (a) Imada, Y.; Iida, H.; Ono, S.; Murahashi, S. J. Am. Chem. Soc. 2003, 125, 2868-2869. (b) Bonesi, S. M.; Manet, I.; Freccero, M.; Fagnoni, M.; Albini, A. Chem. Eur. J. 2006, 12, 4844-4857. (c) Baciocchi, E.; Chiappe, C.; Del Giacco, T.; Fasciani, C.; Lanzalunga, O.; Lapi, A.; Melai, B. Org. Lett. 2009, 11, 1413-1416. (d) Gu, X.; Li, X.; Chai, Y.; Yang, Q.; Li, P.; Yao, Y. Green Chem. 2013, 15, 357360. (e) To, W.; Liu, Y.; Lau, T.; Che, C. Chem. Eur. J. 2013, 19, 5654-5664. (f) Liu, Y.; Howarth, A. J.; Hupp, J. T.; Farha, O. K. Angew. Chem. Int. Ed. 2015, 54, 9001-9005. (g) Neveselý, T.; Svobodov. E.; Chudoba, J.; Sikorski, M.; Cibulkaa, R. Adv. Synth. Catal. 2016, 358, 1654-1663. (19) (a) Qiao, Z.; Liu, H.; Xiao, X.; Fu, Y.; Wei, J.; Li, Y.; Jiang, X. Org. Lett. 2013, 15, 2594-2597. (b) Qiao, Z.; Wei, J.; Jiang, X. Org. Lett. 2014, 16, 1212-1215. (c) Li, Y.; Pu, J.; Jiang, X. Org. Lett. 2014, 16, 2692-2695. (d) Zhang, Y.; Li, Y.; Zhang, X.; Jiang, X. Chem. Commun. 2015, 51, 941-944. (e) Qiao, Z.; Ge, N.; Jiang, X. Chem. Commun. 2015, 51, 10295-10298. (f) Li, Y.; Xie, W.; Jiang, X. Chem. Eur. J. 2015, 21, 16059-16065. (g) Wei, J.; Li, Y.; Jiang, X. Org. Lett. 2016, 18, 340-343. (h) Qiao, Z.; Jiang, X. Org. Lett. 2016, 18, 15501553. (i) Wang, M.; Fan, Q.; Jiang, X. Org. Lett. 2016, 18, 5756-5759. (j) Xiao, X.; Feng, M.; Jiang. X. Angew. Chem. Int. Ed. 2016, 55, 14121-14124. (k) Wang, M.; Wei, J.; Fan, Q.; Jiang, X. Chem. Commun. 2017, 53, 2918-2921. (l) Tan, W.; Wei, J.; Jiang, X. Org. Lett. 2017, 19, 2166-2169. Reviews: (a) Jiang, X. Phosphorus Sulfur Silicon Relat. Elem. 2017, 192, 169-171. (b) Qiao, Z.; Jiang, X. Org. Biomol. Chem. 2017, 15, 1942-1946. (20) Enthaler, S.; Wu, X. Zinc Catalysis-Applications in Organic Synthesis, Wiley-VCH, Weinheim, 2015. (21) CCDC-1541117 (3u): C 13 H 11 BrO 2 S, MW = 311.19, Triclinic, space group P2 1 /n, final R indices [I > 2σ(I)], R 1 = 0.0321, wR 2 = 0.0855, R indices (all data), R 1 = 0.0375, wR 2 = 0.0893, a, = 6.6244(3) Å , , b = 9.5477(5) Å, c = 11.0255(5) Å, α = 69.7280(10) o, β = 77.3960(10)o , , γ = 74.1380(10)o, V = 623.31(5) Å3, Z = 2, Reflections collected/unique: 7271/2171 (R (int) = 0.0212). These data can be obtained free of charge from Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/ci. (22) (a) Rane, R.; Naithani, S.; Natikar, R. D.; Verma, S.; Arulmoli, T. WO2012/70069 A2. (b) Cortes, E.; Mendoza, R.; Gutierrez, M.; De Cortes, O. J. Heterocylic Chem. 2004, 41, 273-276. (23) Bigley, A. N.; Xiang, D.; Ren, Z.; Xue, H.; Hull, K. G.; Romo, D.; Raushel. F. M. J. Am. Chem. Soc. 2016, 138, 2921-2924.
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