Visible-Light-Enabled Aerobic Denitrative C3-Alkenylation of Indoles with β-Nitrostyrenes

Ruchi Chawla; Ritu Kapoor; Lal Dhar S. Yadav

doi:10.1055/s-0040-1707099

Synlett, Table of Contents

Synlett 2020; 31(14): 1394-1399
DOI: 10.1055/s-0040-1707099

letter

Visible-Light-Enabled Aerobic Denitrative C3-Alkenylation of Indoles with β-Nitrostyrenes

Ruchi Chawla

^aPolymer Research Laboratory, Department of Chemistry, Motilal Nehru National Institute of Technology Allahabad, Prayagraj, 211004, India

,

Ritu Kapoor

^bGreen Synthesis Lab, Department of Chemistry, University of Allahabd, Prayagraj 211002, India Email: ldsyadav@hotmail.com

,

Lal Dhar S. Yadav∗

^aPolymer Research Laboratory, Department of Chemistry, Motilal Nehru National Institute of Technology Allahabad, Prayagraj, 211004, India

^bGreen Synthesis Lab, Department of Chemistry, University of Allahabd, Prayagraj 211002, India Email: ldsyadav@hotmail.com

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Abstract

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Abstract

Herein, we unveil the first visible-light-mediated alkenylation reaction of indoles. The reaction follows a denitrative radical pathway where β-nitrostyrenes have been utilized as the alkene precursors for the C3-styrenylation of indoles under visible-light irradiation to afford biologically and synthetically important 3-alkenylindoles. High regioselectivity, absence of any photocatalyst, metal, external oxidant, acid or base, and the use of visible light and air as inexpensive clean reagents are the key highlights of the developed method.

Key words

indoles - β-nitrostyrenes - 3-alkenylindoles - visible light - radical reaction - photocatalyst-free

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References

References and Notes
1 Baeyer A, Emmerling A. Ber. Dtsch. Chem. Ges. 1869; 2: 679

2a Cacchi S, Fabrizi G. Chem. Rev. 2005; 105: 2873
2b Humphrey GR, Kuethe JT. Chem. Rev. 2006; 106: 2875
2c Bandini M, Eichholzer A. Angew. Chem. Int. Ed. 2009; 48: 9608
2d Petrini M. Chem. Eur. J. 2017; 23: 16115
2e Festa AA, Voskressensky LG, Van der Eycken EV. Chem. Soc. Rev. 2019; 48: 4401

3a Sashidhara KV, Dodda RP, Sonkar R, Palnati GR, Bhatia G. Eur. J. Med. Chem. 2014; 81: 499
3b Dolusic E, Larrieu P, Moineaux L, Stroobant V, Pilotte L, Colau D, Pochet L, Van den Eynde B, Masereel B, Wouters J, Frederick R. J. Med. Chem. 2011; 54: 5320
3c Corigliano DM, Syed R, Messineo S, Lupia A, Patel R, Reddy CV. R, Dubey PK, Colica C, Amato R, Sarro GD, Alcaro S, Indrasena A, Brunetti A. PeerJ 2018; 6: 5386
3d Lafayette EA, de Almeida SM. V, Cavalcanti Santos RV, de Oliveira JF, Amorim CA. D. C, da Silva RM. F, Pitta MG. D. R, Pitta ID. R, de Moura RO, de Carvalho Júnior LB, de Melo Rêgo MJ. B, de Lima MD. C. A. Eur. J. Med. Chem. 2017; 136: 511
3e Ozdemir A, Altıntop MD, Turan-Zitouni G, Çiftçi GA, Ertorun I, Alatas O, Kaplancıklı ZA. Eur. J. Med. Chem. 2015; 89: 304
3f Jin G, Lee S, Choi M, Son S, Kim G.-W, Oh J.-W, Lee C, Lee K. Eur. J. Med. Chem. 2014; 75: 413

4a Yoon TP, Ischay MA, Du J. Nat. Chem. 2010; 2: 527
4b Narayanam JM, Stephenson CR. Chem. Soc. Rev. 2011; 40: 102
4c Prier CK, Rankic DA, MacMillan DW. C. Chem. Rev. 2013; 113: 5322
4d Romero NA, Nicewicz DA. Chem. Rev. 2016; 116: 10075
4e Chen JR, Hu XQ, Lu LQ, Xiao WJ. Acc. Chem. Res. 2016; 49: 1911
4f Zhou Q.-Q, Zou Y.-Q, Lu L.-Q, Xiao W.-J. Angew. Chem. Int. Ed. 2019; 58: 1586

5a Pettersson B, Hasimbegovic V, Bergman J. J. Org. Chem. 2011; 76: 1554
5b Tsou H.-R, MacEwan G, Birnberg G, Zhang N, Brooijmans N, Toral-Barza L, Hollander I, Ayral-Kaloustian S, Yu K. Bioorg. Med. Chem. Lett. 2010; 20: 2259

6a Zheng H, He P, Liu Y, Zhang Y, Liu X, Lin L, Feng X. Chem. Commun. 2014; 50: 8794
6b Enders D, Joie C, Deckers K. Chem. Eur. J. 2013; 19: 10818
6c Tan B, Hernández-Torres G, Barbas CF. III. J. Am. Chem. Soc. 2011; 133: 12354
6d Gioia C, Hauville A, Bernardi L, Fini F, Ricci A. Angew. Chem. Int. Ed. 2008; 47: 9236
6e Shih JL, Nguyen TS, May JA. Angew. Chem. Int. Ed. 2015; 54: 9931
6f Kochanowska-Karamyan AJ, Hamann MT. Chem. Rev. 2010; 110: 4489
6g Schmidt AW, Reddy KR, Knölker H.-J. Chem. Rev. 2012; 112: 3193
6h McCabe SR, Wipf P. Org. Biomol. Chem. 2016; 14: 5894
6i Wallwey C, Li S.-M. Nat. Prod. Rep. 2011; 28: 496

7 Jia C, Lu W, Kitamura T, Fujiwara Y. Org. Lett. 1999; 1: 2097

8a Grimster NP, Gauntlett C, Godfrey CR. A, Gaunt MJ. Angew. Chem. Int. Ed. 2005; 44: 3125
8b Chen W.-L, Gao Y.-R, Mao S, Zhang Y.-L, Wang Y.-F, Wang Y.-Q. Org. Lett. 2012; 14: 5920
8c Huang Q, Song Q, Cai J, Zhang X, Lin S. Adv. Synth. Catal. 2013; 355: 1512
8d Verma AK, Jha RR, Chaudhary R, Tiwari RK, Danodia AK. Adv. Synth. Catal. 2013; 355: 421
8e Gemoets HP. L, Hessel V, Noël T. Org. Lett. 2014; 16: 5800
8f Jia K.-Y, Yu J.-B, Jiang Z.-J, Su W.-K. J. Org. Chem. 2016; 81: 6049
8g Kannaboina P, Kumar KA, Das P. Org. Lett. 2016; 18: 900
8h Paul A, Chatterjee D, Banerjee S, Yadav S. Beilstein J. Org. Chem. 2020; 16: 140

9a Xiang S.-K, Zhang B, Zhang L.-H, Cui Y, Jiao N. Chem. Commun. 2011; 47: 8097
9b Sahu S, Banerjee A, Maji MS. Org. Lett. 2017; 19: 464

10a Gao M, Tian J, Lei A. Chem. Asian J. 2014; 9: 2068
10b Volla CM. R, Atodiresei I, Rueping M. Chem. Rev. 2014; 114: 2390
10c Lancianesi S, Palmieri A, Petrini M. Chem. Rev. 2014; 114: 7108
10d Talalay P, De Long MJ, Prochaska HJ. Proc. Natl. Acad. Sci. U.S.A. 1988; 85: 8261
10e Lo JC, Gui J, Yabe Y, Pan C.-M, Baran PS. Nature 2014; 516: 343
10f Kim JH, Kim JH, Lee GE, Lee JE, Chung IK. Mol. Pharmacol. 2003; 63: 1117
10g Yan G, Borah AJ, Wang L. Org. Biomol. Chem. 2014; 12: 6049

11a Jang Y.-J, Shih Y.-K, Liu J.-Y, Kuo W.-Y, Yao C.-F. Chem. Eur. J. 2003; 9: 2123
11b Yao C.-F, Chu C.-M, Liu J.-T. J. Org. Chem. 1998; 63: 719
11c Liu J.-Y, Liu J.-T, Yao C.-F. Tetrahedron Lett. 2001; 42: 3613
11d Zhang N, Quan Z.-J, Zhang Z, Da Y.-X, Wang X.-C. Chem. Commun. 2016; 52: 14234
11e Wagh G, Autade S, Patil PC, Akamanchi KG. New J. Chem. 2018; 42: 3301
11f Tripathi S, Kapoor R, Yadav LD. S. Adv. Synth Catal. 2018; 360: 1407
11g Tripathi S, Yadav LD. S. New J. Chem. 2018; 42: 3765
11h Yadav AK, Singh KN. New J. Chem. 2017; 41: 14914
11i Cai X.-H, Zhang H, Guo H. Curr. Org. Chem. 2019; 23: 1131

12a Ding W, Zhou QQ, Xuan J, Li TR, Lu LQ, Xiao WJ. Tetrahedron Lett. 2014; 55: 4648
12b Yadav S, Srivastava M, Rai P, Tripathi BP, Mishra A, Singh J, Singh J. New J .Chem. 2016; 40: 9694
12c Rathore V, Kumar S. Green Chem. 2019; 21: 2670
12d Yu Z.-Y, Zhao J.-N, Yang F, Tang X.-F, Wu Y.-F, Ma C.-F, Song B, Yun L, Meng Q.-W. RSC Adv. 2020; 10: 4825

13a Singh AK, Chawla R, Yadav LD. S. Tetrahedron Lett. 2015; 56: 653
13b Kapoor R, Chawla R, Yadav LD. S. Tetrahedron Lett. 2019; 60: 805
13c Chawla R, Yadav LD. S. Org. Biomol. Chem. 2019; 17: 4761

14a Rai A, Yadav LD. S. Org. Biomol. Chem. 2011; 9: 8058
14b Rai A, Yadav LD. S. Tetrahedron 2012; 68: 2459
14c Chawla R, Rai A, Singh AK, Yadav LD. S. Tetrahedron Lett. 2012; 53: 5323
14d Keshari T, Kapoorr R, Yadav LD. S. Eur. J. Org. Chem. 2016; 2695

15 Fekarurhobo GK, Angaye SS, Obomann FG. J. Emerging Trends Eng. Appl. Sci. 2013; 4: 394
16 Mohr L.-M, Bauer A, Jandl C, Bach T. Org. Biomol. Chem. 2019; 17: 7192
17 General Procedure for the Synthesis of 3-Alkenylindoles 3 A mixture of indole 1 (1.5 mmol) and β-nitrostyrene (2, 1.0 mmol) in CH₃CN (3 mL) was irradiated with visible light (white-light-emitting diode, 7.0 W) at a distance of 0.75 cm in a 10 mL round-bottom flask with stirring at r.t. for 18 h. Upon completion of the reaction (monitored by TLC), water (5 mL) was added, and the mixture was extracted with EtOAc (3 × 15 mL). The combined organic phases were dried with anhydrous Na₂SO₄, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (EtOAc/n-hexane, 1:19) to afford an analytically pure sample of 3-alkenylindole 3. Characterization Data of Representative 3-Alkenylindoles 3 (E)-3-(4-Methoxystyryl)-1H-indole (3c) ^18,9b ¹H NMR (400 MHz, DMSO): δ = 11.25 (s, 1 H), 7.98 (d, J = 8.0 Hz, 1 H), 7.58 (d, J = 2.4 Hz, 1 H), 7.50 (d, J = 8.8 Hz, 2 H), 7.42 (d, J = 8.0 Hz, 1 H), 7.26 (d, J = 16.6 Hz, 1 H), 7.15 (t, J = 7.6 Hz, 1 H), 7.10 (t, J = 6.9 Hz, 1 H), 7.04 (d, J = 16.4 Hz, 1 H), 6.92 (d, J = 8.2 Hz, 2 H), 3.76 (s, 3 H). ¹³C NMR (100 MHz, DMSO): δ = 158.0, 137.0, 131.2, 126.6, 125.3, 125.2, 123.2, 121.7, 120.3, 119.8, 119.5, 114.1, 113.9, 111.9, 55.1. HRMS (ESI): m/z calcd for C₁₇H₁₆NO [M + H]⁺: 250.1226; found: 250.1196. 3-[(E)-2-(Thiophen-2-yl)vinyl]-1H-indole (3i) ^18,19 ¹H NMR (400 MHz, DMSO): δ = 11.34 (s, 1 H), 7.94 (d, J = 7.6 Hz, 1 H), 7.64 (s, 1 H), 7.41 (d, J = 7.6 Hz, 1 H), 7.32–7.31 (m, 2 H), 7.17–7.10 (m, 4 H), 7.01 (s, 1 H). ¹³C NMR (100 MHz, DMSO): δ = 144.1, 137.0, 127.8, 126.4, 124.9, 124.3, 123.0, 122.3, 121.8, 119.8, 119.7, 117.1, 113.2, 111.9. HRMS (ESI): m/z calcd for C₁₄H₁₂NS [M + H]⁺: 226.0685; found: 226.0681. (E)-5-Fluoro-3-styryl-1H-indole (3l) ¹⁹ ¹H NMR (400 MHz, DMSO): δ = 11.47 (s, 1 H), 7.82 (d, J = 10.0 Hz, 1 H), 7.75 (s, 1 H), 7.60 (d, J = 7.2 Hz, 2 H), 7.45–7.41 (m, 2 H), 7.35 (t, J = 6.8 Hz, 2 H), 7.19 (t, J = 6.6 Hz, 1 H), 7.10 (d, J = 17.1 Hz, 1 H), 7.03 (t, J = 8.4 Hz, 1 H). ¹³C NMR (100 MHz, DMSO): δ = 159.0, 138.9, 134.0, 129.0, 128.1, 126.7, 126.0, 125.8, 123.9, 122.4, 114.4, 113.3, 110.4, 105.3. HRMS (ESI): m/z calcd for C₁₆H₁₃FN [M + H]⁺: 238.1027; found: 238.1007.
18 Low KH, Magomedov NA. Org. Lett. 2005; 7: 2003
19 Guan X.-K, Liu G.-F, An D, Zhang H, Zhang S.-Q. Org. Lett. 2019; 21: 5438

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