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BY 4.0 license Open Access Published by De Gruyter March 11, 2021

Lewis acid / Base-free Strategy for the Synthesis of 2-Arylthio and Selenyl Benzothiazole / Thiazole and Imidazole

  • Guniganti Balakishan , Gullapalli Kumaraswamy EMAIL logo , Vykunthapu Narayanarao and Pagilla Shankaraiah

Abstract

A Cu(II)-catalyzed Csp2-Se and Csp2-Sulfur bond formation was achieved with moderate to good yields without the aid of Lewis acid and base. The reaction is compatible with a wide range of heterocycles such as benzothiazole, thiazole, and imidazole. Also, this typical protocol is found to be active in thio-selenation via S-H activation. Additionally, we proposed a plausible mechanistic pathway involving Cu(III) putative intermediate.

Introduction

Organoselenium scaffolds engrossed much attention from chemists owing to their varied pharmaceutical activity such as antioxidants [1,2,3,4,5], anti-inflammatory [6,7,8], and antimicrobial agents [9]. Additionally, the organoselenium molecular entities were assessed for anticancer [1011], neuroprotective [12], and antiviral properties [1314]. Recently, selenium-containing molecules have gained a great deal of significance due to the optical activities of organic materials [1516].

The functionalization of C–H bonds adjacent to a hetero-atom utilizing cross-coupling is a conceptually ideal process. Also, this strategy represents an extremely attractive and competent route for the substitution of C–H bond. Moreover, the strategy is considered to be straightforward and has a step-economic advantage than traditional reactions [1718]. Primarily, this process was induced by a sub-stoichiometric transition metal in combination with additives and bases. This regioselective oxidative coupling strategy enabled the synthesis of various pharmaceutically active heterocyclic molecular motifs [19,20,21]. Various groups have reported the cross-coupling of C–H bonds adjacent to a nitrogen atom to give new C–C, C-X (X = S, Se, and Te) bond containing molecules. In particular, the construction of new C–S and C-Se bonds via oxidative functionalization of a C(sp2)-H bond of benzothiazoles, thiazoles, benzoxazoles, azoles, benzimidazole, imidazole, and oxadiazole has been reported elegantly [22,23,24,25,26,27,28,29]. Amongst such strategies, a Lewis acid-catalyzed, stoichiometric Cu(II)-mediated thiolation reaction between heteroarenes and thiols strategy offers an appealing alternative to the conventional methods [30] (Scheme 1).

Scheme 1 Previous routs for selenation and thiolation of C–H bonds adjacent to a hetero-atom
Scheme 1

Previous routs for selenation and thiolation of C–H bonds adjacent to a hetero-atom

However, all these methods require stoichiometric amounts of external oxidants and bases. Hence, there is still a great need for the development of sole oxidant as air and base free protocol to produce various thioaryl and selenoaryl derivatives of benzothiazoles, thiazoles, azoles, benzimidazole, and imidazole.

Results and discussion

In our continuous interest in developing base-free Cu catalyzed reactions [31,32,33,34], we assessed the direct selenation and thiolation of benzothiazole. Initially, conducting the reaction between benzothiazole 1a (1 equiv.) and diphenyl diselenide 2a (1.2 equiv.) in the presence of Cu(OAc)2 reaction under otherwise identical condition gave the product 3a in 70% yield (Table 1, Entry 2).

Table 1

Optimization of reaction conditions for direct selenationa

Table 1 Optimization of reaction conditions for direct selenationa
Entry Catalyst Solvent 3a (% yield)c
1 Cu(OAc)2 (100 mol%) dioxane 54
2 Cu(OAc)2 (50 mol%) dioxane 70
3 Cu(OAc)2 (20 mol%) dioxane 86
4 Cu(OAc)2 (10 mol%) dioxane 56
5 Cu(OAc)2 (20 mol%) dioxane 86b,d
6 Cu(OAc)2 (20 mol%) (CH2Cl2)2 40
7 Cu(OAc)2 (20 mol%) CH3CN 60
8 Cu(OAc)2 (20 mol%) DMF 35
9 Cu(OAc)2 (20 mol%) DMSO 40
10 Cu(OAc)2 (20 mol%) H2O 20
11 Cu(OAc)2 (20 mol%) neat 40
12 CuI(20 mol%) dioxane 20
13 CuOTf(20 mol%) dioxane 25
14 CuCl2(20 mol%) dioxane 20
15 Cu(CH3CN)4PF6(20 mol%) dioxane 30
16 Co(OAc)2 (20 mol%) dioxane NRe
17 Pd(OAc)2 (20 mol%) dioxane NRe
  1. a)

    All reactions were carried out unless otherwise stated on the 1 mmol scale with 1.0 equiv. 1a and 1.1 equiv. of 2a in 2 mL of dioxane heating at 100 °C for 5 h in the open air.

  2. b)

    The reaction was carried out with 1.0 equiv. 1a and 0.6 equiv. of 2a.

  3. c)

    Isolated yield but not optimized. Yields based on the disappearance of 2a.

  4. d)

    This reaction was also carried out at 10 mmol scale.

  5. e)

    NR = No reaction.

In another reaction, the increased yield of 3a was observed with 20 mol% of Cu(OAc)2 under the same set of conditions (Table 1, Entry 3). A reaction with 10% Cu(OAc)2 loading under typical conditions afforded 3a in a decreased yield (Table 1, Entry 4). Interestingly, it was observed that the diphenyl diselenide 2a was not completely consumed (vide-supra) and the unreacted 2a was recovered at a yield of 40%. When 2a molar ratio was reduced from 1.0 mmol to 0.6 mmol and carried out under identical conditions as above, this resulted in 3a with similar yields (Table 1, Entry 5). This result indicates that the by-product PhSeH re-oxidized to PhSeSePh under the atmosphere of air. Hence, it needs in an only half-molar equivalent. After considerable experimentation, we established that benzothiazole 1a (1 equiv.), diphenyl diselenide 2a (0.6 equiv.) and 20 mol% of Cu(OAc)2 in 1,4-dioxane at 100 °C for 5 h was most effective set of conditions, yielding the 3a at yield of 86% (Table 1, Entry 5).

Among the solvents tested, only 1,4-dioxane gave a better yield of the desired compound 3a while other solvents, such as ClCH2CH2Cl, CH3CN, DMF, DMSO, and H2O gave a lower yield of 3a (Table 1, Entries 6 to 10). Interestingly, the reaction proceeded without solvent but with albeit inferior yield (Table 1, Entry 11). A screening of copper salts indicated that Cu(OAc)2.H2O performed with good efficiency for this transformation, while CuI and CuOTf, CuCl2, and Cu(CH3CN)4PF6 led to inferior yields of 3a (Table 1, Entries 11 to 15). The Co(OAc)2 and Pd(OAc)2 as catalyst failed to initiate the reaction (Table 1, Entries 16–17). The reaction performed under an air balloon and oxygen balloon gave 3a in trace amount. To demonstrate the viability of this protocol, a scale-up reaction at 10 mmol levels had also been conducted and the desired product 3a was obtained with a similar yield.

Furthermore, the reaction scope was extended by employing typical conditions and the results are shown in Table 2. To this end, N-methyl benzimidazole 1b and N-ethyl benzimidazole 1c reacted in the presence of 2a using similar conditions. The expected products 3b and 3c were isolated in 87% and 82% yields, respectively (Table 2, Entry 1). Likewise, N-methyl imidazole 1d and N-phenyl imidazole 1e reacted smoothly in the presence of 2a under standard protocol and the corresponding products 3d and 3e were isolated in 86% and 85% yields, correspondingly (Table 2, Entry 2). Remarkably, under optimized conditions, the substrates 4-methyl thiazole 1f and 5-methyl-4-vinylthiazole 1g showed good reactivity with 2a in the presence of Cu(AcO)2 and provided the seleno derivatives 3f and 3g, in the same way (Table 2, Entries 3 and 4). The significant aspect of the reaction under this oxidative condition is that it sustains a vinyl functionality (Table 2, Entry 4). Furthermore, the direct thiolation protocol was also achieved using typical selenation conditions. Then, benzothiazole 1a, N-methyl benzimidazole 1b, 4-methyl thiazole 1h and 2-phenyl-1, 3, 4-oxadiazole were subjected to direct thiolation protocol using 2b. As expected, the thiolation products 3h-k were furnished in good to high yields demonstrating the generality of this reaction (Table 2, Entries 5-8).

Table 2

Copper catalyzed synthesis of selenium and sulphur containing heterocycles

Entry Substrate Producta,b,c (%Yield) Entry Substrate Producta,b,c (%Yield)
1 5
2 6
3 7
4 8
  1. a)

    All reactions were carried out unless otherwise stated on the 1 mmol scale with 1.0 equiv. 1a–i and 0.6 equiv. of 2a and 2b in 2 mL of dioxane heating at 100 °C for 5 h in the open air.

  2. b)

    Isolated yield but not optimized. Yields based on the disappearance of 2a and 2b.

  3. c)

    All products fully characterized by 1H-NMR, 13C-NMR, IR, and Mass.

Next, we intended to explore Cu-catalyzed S-H activation and trap the resulting organo-copper intermediate with diphenyl diselenide 2a under established protocol as above. Under the typical procedure, the substrates 4a–c were submitted for S-H activation. To our delight, all the substrates underwent reaction and the expected 2-phenylselenothio derivatives 5a–c were isolated at a yield of 80%, 70%, and 80%, respectively (Table 3, Entries 1–3). Interestingly, this method represents a novel and mild method for the preparation of organo-sulfur-selenium containing heterocycles.

Table 3

Synthesis of sulphur-selenium heterocycles via oxidative copper catalysis

Table 3 Synthesis of sulphur-selenium heterocycles via oxidative copper catalysis
Entry R R-S-Se-Pha,b,c (Yield)
1
2
3
  1. a)

    All reactions were carried out unless otherwise stated on the 1 mmol scale with 1.0 equiv. 4a–c and 0.6 equiv. of 2a in 2 mL of dioxane heating at 100 °C for 5 h in the open air.

  2. b)

    Isolated yield but not optimized. Yields based on the disappearanceof 2a.

  3. c)

    All products fully characterized by 1H-NMR, 13C-NMR, IR, and Mass.

In light of this work, we now propose the following mechanism (Scheme 2). At first, copper insertion leads to the active intermediate A which activates benzothiazole resulting in a Cu-thiolate complex and concomitant abstraction of a C-H by releasing AcOH and the copper (II) complex B. The copper (II) complex of B undergoes oxidation via disproportion to form Cu(III)-complex C [35]. Then, reductive elimination of Cu(I)OAc liberates the desired product. The Cu(I)OAc undergoes further oxidation in the presence of air and AcOH to form copper(II) acetate. A similar mechanistic pathway can be expected to perform in the synthesis of sulfur-selenium heterocycles of 5a–c. This hypothesis needs further study.

Scheme 2 Plausible catalytic cycle for the direct selenation
Scheme 2

Plausible catalytic cycle for the direct selenation

Conclusion

In conclusion, this study may contribute to a refinement of the cross-coupling of C–H bonds, in particular, adjacent to a nitrogen atom to give new C-X (X = S and Se) bond containing molecules. Furthermore, the significant practical advantage is circumventing the stoichiometric use of base and oxidant. This protocol provides an alternative expedient synthesis of chalcogenide containing heterocyclic bioactive molecules. In particular, the synthesis of sulfur-selenium heterocycles via oxidative copper catalysis is the first of its kind to the best of our knowledge. Further work is under progress towards this end in our laboratory.

Experimental Section

All reactions were conducted under an open-air atmosphere. Apparatus used for reactions are oven-dried. 1,4-dioxane and other solvents were used as received. 1H-NMR spectra were recorded at 300, 400 and 500 MHz and 13C-NMR at 75 and 125 MHz in CDCl3. J values were recorded in hertz and abbreviations used were s = singlet, d = doublet, m = multiplet, br = broad, dd = doublet of doublet. Chemical shifts (δ) are reported relative to TMS (δ = 0.0) as an internal standard. IR (FT-IR) spectra were measured as KBr pellets or as films. Mass spectral data were compiled using MS (ESI), HR-MS mass spectrometers. Column chromatography was carried out using Silica gel 100–200 mesh (commercial suppliers).

A typical procedure for the Synthesis of 2-phenylseleno benzothiozole (3a): Benzothizole 1a (1.0 mmol), diphenyl diselinide (0.6 mmol), and Cu(OAc)2.H2O (0.2 mmol, 20 mol%) were charged sequentially into a 10 mL round-bottomed flask. To this, 1,4-dioxane (5 mL) was added and the resulting reaction mixture was stirred at 100 °C for 5 h. Then, cooled to ambient temperature and the solvent was evaporated to give a residue that was purified over silica gel column chromatography eluting with hexane / EtOAc (9:1) to give the desired product 3a (185 mg, 86%) as a yellow solid, mp. 38–40 °C, lit. [22] 35–36 °C. 1H-NMR (500MHz, CDCl3): δ 7.90 (d, 1H, J = 8.2 Hz), 7.80 (d, 2H, J = 8.0 Hz), 7.70 (d, 1H, J = 7.6 Hz), 7.40–7.50 (m, 4H), 7.26–7.29 (m, 1H). 13C-NMR (75MHz, CDCl3): δ 162.7, 154.5, 136.6, 130.0, 129.9, 126.5, 125.9, 124.3, 121.9, 120.7. IR (KBr): 3056, 2969, 2923, 2851, 1739, 1453, 1418, 1368, 1307, 1067, 1018, 968, 851, 737, 686 cm−1. MS (ESI): 291 (M+H). HR-MS (m/z): Calculated for C19H19NSSe (M+H) = 291.9684. Found (M+H) = 291.9693.

All other compounds including the sulfur-selenium heterocycles were synthesized 1mmol scale employing above typical procedure.

1-Methyl-2-(phenylselenyl)-1H-benzo(d)imidazole (3b) (Table 2, Entry 1): Yellow solid, yield 190 mg (87%), mp. 58–62 °C. 1H-NMR (500MHz, CDCl3): δ 7.80 (d, 1H, J = 8.2 Hz), 7.50–7.52 (m, 2H), 7.20–7.30 (m, 6H), 3.70 (s, 3H). 13C-NMR (75MHz, CDCl3): δ 143.6, 142.7, 136.0, 132.4, 129.6, 128.0, 123.4, 124.3, 122.5, 119.4, 109.5, 31.8. IR (KBr): 3019, 1710, 1661, 1628, 1549, 1515, 1214, 742, 667, 627 cm−1. MS (ESI): 291 (M+H). HR-MS: Calculated for C14H12N2Se (M+H) = 289.0238. Found (M+H) = 289.0231.

Ethyl-2-(phenylselenyl)-1H-benzo(d)imidazole (3c) (Table 2, Entry 1): Dense liquid, yield 170 mg (82%). 1H-NMR (500MHz, CDCl3): δ 7.80–7.84 (m, 1H), 7.50–7.56 (m, 2H), 7.20–7.31 (m, 6H), 4.32 (q, J = 7.3 Hz, 2H), 1.24 (t, J = 7.3 Hz, 3H). 13C-NMR (75MHz, CDCl3): δ 143.6, 142.9, 135.1, 132.4, 129.6, 128.0, 123.2, 118.9.109.6, 40.6, 14.8. IR (neat): 3055, 2977, 2927, 2852, 1609, 1576, 1414, 1343, 1251, 1152, 1102, 1067, 1020, 772, 737, 688, 668 cm−1. MS (ESI): 303 (M+H). HR-MS: Calculated for C15H14N2Se (M+H) = 303.0395. Found = 303.0387.

1-Methyl-2-(Phenylselenyl)-1H-imidazole (3d) (Table 2, Entry 2): Yellow liquid, yield 250 mg (86%). 1H-NMR (500MHz, CDCl3): δ 7.31–7.00 (m, 7H), 3.60 (s, 3H). 13C-NMR (75MHz, CDCl3): δ 133.9, 130.5, 130.1, 129.3, 126.9, 123.7, 34.7. IR (neat): 2922, 2851, 1576, 1476, 1451, 1441, 1408, 1277, 1219, 1113, 1067, 1021, 913, 772, 687 cm−1. MS (ESI): 239 (M+H). HR-MS: Calculated for C10H10N2Se (M+H) = 239.0082. Found = 239.0077.

1-Phenyl-2-(phenylselenyl)-1H-imidazole (3e) (Table 2, Entry 2): Yellow liquid, yield 180 mg (86%). 1H-NMR (500MHz, CDCl3): δ 7.40–7.10 (m, 12H). 13C-NMR(75MHz, CDCl3): δ 132.2, 130.9, 129.2, 128.1, 128.5, 127.4, 126.2. IR (neat): 2921, 2852, 1730, 1597, 1498, 1458, 1422, 1300, 1219, 1078, 968, 772, 690 cm−1. MS (ESI): 301 (M+H). HR-MS: Calculated for C15H12N2Se (M+H) = 301.9684. Found = 301.9693.

4-Methyl-2-(phenylselenyl)thiazole (3f) (Table 2, Entry 3): Yellow liquid, yield 220 mg (85%). 1H-NMR (500MHz, CDCl3): δ 7.58–7.60 (m, 2H), 7.38–7.40 (m, 2H), 7.21 (s, 1H), 6.70 (s,1H), 2.41 (s, 3H). 13C-NMR (75MHz, CDCl3): δ 156.3, 154.4 134.9, 132.0, 129.6, 129.0, 128.2, 116.6, 17.0. IR (neat): 3019, 1710, 1661, 1628, 1549, 1515, 1214, 742, 667, 627 cm−1. MS (ESI): 256 (M+H). HR-MS: Calculated for C10H9NS Se (M+H) = 256.0249. Found = 256.0250.

5-Methyl-2-(phenylselenyl)-4-vinylthiazole (3g) (Table 2, Entry 4): Yellow liquid, yield 180 mg (80%). 1H-NMR (500MHz, CDCl3): δ 7.69–7.70 (m, 2H), 7.31–7.40 (m, 2H), 7.2 (s, 1H), 6.6 (q, 1H, J = 11.3 Hz), 5.1 (q, 1H, J = 17.3 Hz), 2.38 (s, 3H). 13C-NMR (75MHz, CDCl3): δ 180.0, 136.0, 135.0, 135.0, 130.6, 130.3, 129.7, 129.2, 15.2. IR(neat): 2922, 2852, 1657, 1576, 1475, 1438, 1401, 1375, 1301, 1219, 1018, 999, 772,689 cm−1. MS (ESI): 282 (M+H). HR-MS: Calculated for C12H11NSSe (M+H) = 282.1021. Found = 282.1017.

2-(Phenylthio)benzo(d)thiazole (3h) (Table 2, Entry 5): Yellow liquid, Yield 140 mg (77%). 1H-NMR (500MHz, CDCl3): δ 7.28 (t, 1H, J = 7.2 Hz), 7.55–7.40 (m, 4H), 7.66 (d, 1H, J = 8.3 Hz), 7.76 (d, 2H, J = 8.3 H), 7.90 (d, 1H, J = 8.2 Hz). 13C-NMR (75MHz, CDCl3): δ 169.4, 153.6, 135.1, 130.2, 129.7, 125.9, 124.1, 121.7, 120.6. IR(neat): 3019, 1710, 1661, 1628, 1549, 1515, 1214, 742, 667, 627 cm−1. MS (ESI): 244 (M+H). HR-MS: Calculated for C13H9NS2 (M+H) = 244.0249. Found = 244.0244.

1-Methyl-2-(phenylthio)-1H-benzo(d)imidazole (3i) (Table 2, Entry 6): Yellow liquid, yield 150 mg (82%). 1H-NMR (500MHz, CDCl3): δ 7.70 (d, 1H, J = 7.6 Hz), 7.20–7.30 (m, 8H), 3.70 (s, 3H). 13C-NMR (75MHz, CDCl3): δ 142.0, 132.0, 130, 129.4, 129.0, 127.6, 23.2, 122.4, 119.8, 109.0, 30.7. IR (neat): 3056, 2923, 2852, 1741, 1645, 1611, 1581, 1441, 1365, 1277, 1219, 1153, 1110, 1023, 1003, 818, 772, 688, 567 cm−1. MS (ESI): 241 (M+H). HR-MS: Calculated for C14H12N2S (M+H) = 241.0794. Found = 241.0793.

4-Methyl-2-(phenylthio)thiazole (3j) (Table 2, Entry 7): Yellow liquid, yield 175 mg (78%). 1H-NMR (500MHz, CDCl3): δ 7.58–7.60 (m, 2H), 7.38–7.40 (m, 2H), 7.21 (s, 1H), 6.70 (s,1H), 2.41 (s, 3H). 13C-NMR (75MHz, CDCl3): δ 164.7, 153.5 133.5, 132.0, 129.6, 129.3, 115.0, 17.1. IR (neat): 3019.7, 1710, 1661.4, 1628, 1549, 1515.3, 1214.8, 742, 667, 627 cm−1. MS (ESI): 208 (M+H). HR-MS: Calculated for C10H9NS2 (M+H) = 208.0249. Found = 208.0250.

2-Phenyl-5-(phenylthio)-1, 3, 4-oxadiazole (3k) (Table 2, Entry 8): Yellow liquid, yield 140 mg (80%). 1H-NMR (500MHz, CDCl3): δ 7.97–7.90 (m, 2H), 7.69–7.60 (m, 2H), 7.50–7.40 (m, 6H). 13C-NMR (75MHz, CDCl3): δ 166.3, 162.8, 133.6, 131.7, 129.7, 128.9, 126.7, 123.4. IR (neat): 3019, 1710, 1661, 1628, 1549, 1515, 1214, 742, 667, 627 cm−1. MS (ESI): 255 (M+H). HR-MS: Calculated for C14H10N2OS (M+H) = 255.9684. Found = 255.9693.

2-((Phenylselanyl)thio)benzo(d)thiazole (5a) (Table 3, Entry 1): Yellow liquid, yield 155 mg (77%). 1H-NMR (500MHz, CDCl3): δ 7.90 (d, 1H, J = 8.2 Hz), 7.70 (d, 1H, J = 7.6 Hz), 7.50–7.61 (m, 2H), 7.24–7.28 (m,5H). 13C-NMR (75MHz, CDCl3): δ 131.4, 129.8, 129.5, 129.1, 128.9, 127.6, 126.5, 125.2, 122.5, 121.2. IR (neat): 2956, 2918, 2850, 1727, 1462, 1426.3, 1377.8, 1265, 1123, 1077, 1003, 972, 909, 727, 687 cm−1. MS (ESI): 323 (M+H). HR-MS: Calculated for C13H9NSeS2 (M+H) = 323.9414. Found = 323.9409.

2-Phenyl-5-((phenylselanyl)thio)-1,3,4-oxadiazole (5b) (Table 3, Entry 2): Yellow liquid, Yield 160 mg (70%). 1H-NMR (500MHz, CDCl3): δ 7.90 (d, 1H, J = 7.5 Hz), 7.20–7.61 (m, 9H). 13C-NMR (75MHz, CDCl3): δ 133.2, 132.0, 131.4, 129.5, 129.1, 127.6, 126.8. IR(neat): 2919, 2851, 1781, 1726, 1609, 1578, 1576, 1549, 1465, 1349, 1286, 1219, 1170, 1066, 1023, 956, 772, 689 cm−1. MS (ESI): 335 (M+H). HR-MS: Calculated for C14H10N2OSSe (M+H) = 335.1021. Found = 335.1017.

1-Phenyl-5-((phenylselanyl)thio)-1H-tetrazole (5c) (Table 3, Entry 3): Yellow liquid, yield 150 mg (80%). 1H-NMR (500MHz, CDCl3): δ 7.70 (d, 1H, J = 7.5 Hz), 7.60–7.20 (m, 9H). 13C-NMR (75MHz, CDCl3): δ 153.2, 150.9, 149.9, 149.2, 149.1, 149.0, 148.6 147.1, 144.0. IR (neat): 3019, 1710, 1661, 1628, 1549, 1515, 1214, 742, 667, 627 cm−1. MS (ESI): 334 (M+H). HR-MS: Calculated for C13H10N4SSe (M+H) = 334.9864; Found (M+H) = 334.9860.

Acknowledgements

ORGIN program (CSIR) and CSIR (New Delhi) is gratefully acknowledged for awarding the fellowship to G. B and VN.

  1. Supporting Information:

    Copies of 1H and 13C NMR spectra are available.

  2. Research funding:

    Financial support was provided by the DST, New Delhi, India (Grant No: SR/S1/OC-08/2011).

  3. Conflict of interest:

    Authors state no conflict of interest.

  4. Data availability statement:

    All data generated or analyzed during this study are included in this published article and its supplementary information files.

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Received: 2020-01-27
Accepted: 2021-01-27
Published Online: 2021-03-11

© 2021 Guniganti Balakishan et al., published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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