Synlett, Inhaltsverzeichnis Synlett 2024; 35(20): 2385-2390DOI: 10.1055/a-2316-5200 letter Special Issue to Celebrate the 75th Birthday of Prof. B. C. Ranu One-Pot Expeditious Synthesis of Pyrazoloindolones via Base-Promoted Electrocyclization, C–N Coupling and Intramolecular Oxidative Cyclization Harshita Singh Korawat , Manoj Kumar Saini , Karmdeo Prajapati , Maya Shankar Singh ∗ , Ashok Kumar Basak∗ Artikel empfehlen Abstract Artikel einzeln kaufen Alle Artikel dieser Rubrik Abstract Pyrazoloindolones are synthesized from N-tosylhydrazones in a one-pot multistep process which include base-promoted (i) electrocyclization reaction of N-tosylhydrazones derived from α,β-unsaturated aldehydes, (ii) aromatic nucleophilic substitution, and (iii) a domino cyclization–oxidation process under aerobic conditions. Key words Key words N-tosylhydrazone - electrocyclization - aromatic nucleophilic substitution - oxidative cyclization - pyrazoloindolones Volltext Referenzen References and Notes 1a Cherukupalli S, Karpoormath R, Chandrasekaran B, Hampannavar GA, Thapliyal N, Palakollu VN. Eur. J. Med. Chem. 2017; 126: 298 1b Kaswan P, Pericherla K, Purohit D, Kumar A. Tetrahedron Lett. 2015; 56: 549 1c Crossley EL, Issa F, Scarf AM, Kassiou M, Rendina LM. Chem. Commun. 2011; 47: 12179 1d Al-Adiwish WM, Tahir MI. M, Siti-Noor-Adnalizawati A, Hashim SF, Ibrahim N, Yaacob WA. Eur. J. Med. Chem. 2013; 64: 464 1e Selleri S, Bruni F, Costagli C, Costanzo A, Guerrini G, Ciciani G, Gratteri P, Besnard F, Costa B, Montali M, Martini C, Fohlin J, Siena GD, Aiello PM. J. Med. Chem. 2005; 48: 6756 1f Kamal A, Tamboli JR, Nayak VL, Adil SF, Vishnuvardhan MV. P. S. Bioorg. Med. Chem. Lett. 2013; 23: 3208 1g Ahmed OM, Mohamed MA, Ahmed RR, Ahmed SA. Eur. J. Med. Chem. 2009; 44: 3519 1h Reynolds A, Hanani R, Hibbs D, Damont A, Da Pozzo E, Selleri S, Dolle F, Martini C, Kassiou M. Bioorg. Med. Chem. Lett. 2010; 20: 5799 1i James ML, Fulton RR, Vercoullie J, Henderson DJ, Garreau L, Chalon S, Dolle F, Costa B, Guilloteau D, Kassiou M. J. Nucl. Med. 2008; 49: 814 1j Senga K, Novinson T, Springer RH, Rao RP, O’Brien DE, Robins RK, Wilson HR. J. Med. Chem. 1975; 18: 312 1k Xu Y, Brenning BG, Kultgen SG, Foulks JM, Clifford A, Lai S, Cha A, Merx S, McCullar MV, Kanner SB, Ho K.-K. ACS Med. Chem. Lett. 2015; 6: 63 1l Tian Y, Du D, Rai D, Wang L, Liu H, Zhan P, De Clercq E, Pannecouque C, Liu X. Bioorg. Med. Chem. 2014; 22: 2052 1m Dowling JE, Alimzhanov M, Bao L, Block MH, Chuaqui C, Cooke EL, Denz CR, Hird A, Huang S, Larsen NA. ACS Med. Chem. Lett. 2013; 4: 800 2a De Mello H, Echevarria A, Bernardino AM, Canto-Cavalheiro M, Leon LL. J. Med. Chem. 2004; 47: 5427 2b Sekikawa I, Nishie J, Tono-oka S, Tanaka Y, Kakimoto S. J. Heterocycl. Chem. 1973; 10: 931 2c Tucker TJ, Sisko JT, Tynebor RM, Williams TM, Felock PJ, Flynn JA, Lai M.-T, Liang Y, McGaughey G, Liu M, Miller M, Moyer G, Munshi V, Perlow-Poehnelt R, Prasad S, Reid JC, Sanchez R, Torrent M, Vacca JP, Wan B.-L, Yan Y. J. Med. Chem. 2008; 51: 6503 2d Ochiai H, Ishida A, Ohtani T, Kusumi K, Kishikawa K, Yamamoto S, Takeda H, Obata T, Makai H, Toda M. Bioorg. Med. Chem. 2004; 12: 4089 2e Revesz L, Blum E, Di Padova FE, Buhl T, Feifel R, Gram H, Hiestand P, Manning U, Neumann U, Rucklin G. Bioorg. Med. Chem. Lett. 2006; 16: 262 2f Bare TM, McLaren CD, Campbell JB, Firor JW, Resch JF, Walters CP, Salama AI, Meiners BA, Patel JB. J. Med. Chem. 1989; 32: 2561 2g Hoehn H, Polacek I, Schulze E. J. Med. Chem. 1973; 16: 1340 2h Chu I, Lynch BM. J. Med. Chem. 1975; 18: 161 2i Shutske GM, Roehr JE. J. Heterocycl. Chem. 1997; 34: 789 2j Henke BR, Aquino CJ, Birkemo LS, Croom DK. Jr, Ervin GN, Grizzle MK, Hirst GC, James MK, Johnson MF, Queen KL, Sherrill RG, Sugg EE, Suh EM, Szewczyk JW, Unwalla RJ, Yingling J, Willson TM. J. Med. Chem. 1997; 40: 2706 2k Straub A, Benet-Buckholtz J, Frode R, Kern A, Kohlsdorfer C, Schmitt P, Schwarz T, Siefert H.-M, Stasch J.-P. Bioorg. Med. Chem. 2002; 10: 1711 3 Kumar SV, Saraiah B, Parameshwarappa G, Ila H, Verma GK. J. Org. Chem. 2014; 79: 7961 4a Kato K, Suzuki T, Ishihara H. JP 2002167305A 20020611, 2002 4b Hu GQ, Hou LL, Yang Y, Yi L, Xie SQ, Wang GQ, Duan NN, Chao TY, Wen XY, Huang WL. Chin. Chem. Lett. 2011; 22: 804 5a Mata G, Miles DH, Drew SL, Fournier J, Lawson KV, Mailyan AK, Sharif EU, Yan X, Beatty JW, Banuelos J, Chen J, Ginn E, Chen A, Gerrick KY, Pham AT, Wong K, Soni D, Dhanota P, Shaqfeh SG, Meleza C, Narasappa N, Singh H, Zhao X, Jin L, Schindler U, Walters MJ, Young SW, Walker NP, Leleti MR, Powers JP, Jeffrey JL. J. Med. Chem. 2022; 65: 1418 5b Anand D, Yadav P, Patel O, Parmar N, Maurya R, Vishwakarma P, Raju K, Taneja I, Wahajuddin M, Kar S, Yadav P. J. Med. Chem. 2017; 60: 1041 6 Li X, Yu Y, Tu Z. Molecules 2021; 26: 1202 For pyrrolo[1,2-a]indole-based natural products and bioactive molecules, see: 7a Bass PD, Gubler DA, Judd TC, Williams RM. Chem. Rev. 2013; 113: 6816 7b Pousset JL, Cave A, Chiaroni A, Riche C. J. Chem. Soc., Chem. Commun. 1977; 8: 261 7c Fernandez LS, Sykes ML, Andrews KT, Avery VM. Int. J. Antimicrob. Agents 2010; 36 275 7d Fernandez LS, Buchanan MS, Carroll AR, Feng YJ, Quinn RJ, Avery VM. Org. Lett. 2009; 11: 329 7e Zeldin RM, Toste FD. Chem. Sci. 2011; 2: 1706 7f Buzard DJ, Lopez L, Moody J, Kawasaki A, Schrader TO, Kasem M, Johnson B, Zhu X, Thoresen L, Kim SH, Gharbaoui T, Sengupta D, Calvano L, Krishnan A, Gao Y, Semple G, Edwards J, Barden J, Morgan M, Usmani K, Chen C, Sadeque A, Chen W, Christopher RJ, Thatte J, Fu L, Solomon M, Whelan K, Al-Shamma H, Gatlin J, Gaidarov I, Anthony T, Le M, Unett DJ, Stirn S, Blackburn A, Behan DP, Jones RM. ACS Med. Chem. Lett. 2014; 5: 1334 7g Schrader TO, Johnson BR, Lopez L, Kasem M, Gharbaoui T, Sengupta D, Buzard D, Basmadjian C, Jones RM. Org. Lett. 2012; 14: 6306 7h Tanaka M, Ubukata M, Matsuo T, Yasue K, Matsumoto K, Kajimoto Y, Ogo T, Inaba T. Org. Lett. 2007; 9: 3331 7i Wilson RM, Thalji RK, Bergman RG, Ellman JA. Org. Lett. 2006; 8: 1745 7j Liu JF, Jiang ZY, Wang RR, Zheng YT, Chen JJ, Zhang XM, Ma YB. Org. Lett. 2007; 9: 4127 7k Sharma V, Kumar P, Pathak D. J. Heterocycl. Chem. 2010; 47: 491 7l Chadha N, Silakari O. Eur. J. Med. Chem. 2017; 134: 159 7m Norwood IV V. M, Huigens RW. III. ChemBioChem 2019; 20: 2273 7n Mathada BS, Yernale NG, Basha JN. ChemistrySelect 2023; 8: e202204181 7o Schmidt AW, Reddy KR, Knölker H.-J. Chem. Rev. 2012; 112: 3193 7p Miaskiewicz S, Weibel J.-M, Pale P, Blanc A. RSC Adv. 2022; 12: 26966 7q Zhang Z, Yi D, Zhang M, Wei J, Lu J, Yang L, Wang J, Hao N, Pan X, Zhang S, Wei S, Fu Q. ACS Catal. 2020; 10: 10149 7r Somei M, Yamada F. Nat. Prod. Rep. 2004; 21: 278 7s Cacchi S, Fabrizi G. Chem. Rev. 2005; 105: 2873 7t Somei M, Yamada F. Nat. Prod. Rep. 2005; 22: 73 7u Garg NK, Caspi DD, Stoltz BM. J. Am. Chem. Soc. 2005; 127: 5970 7v Humphrey GR, Kuethe JT. Chem. Rev. 2006; 106: 2875 7w Krajewski K, Zhang Y, Parrish D, Deschamps J, Roller PP, Pathak VK. Bioorg. Med. Chem. Lett. 2006; 16 3034 7x Chen Z.-Z, Li S.-Q, Zhang Y.-J, Tang D.-Y, Meng J.-P, Lei J, Li H.-Y, Xu Z.-G. Org. Lett. 2018; 20: 7811 8a Shelke YG, Hande PE, Gharpure SJ. Org. Biomol. Chem. 2021; 19: 7544 8b Ríos M.-C, Portilla J. Chemistry 2022; 4: 940 8c Lv Y, Meng J, Li C, Wang X, Ye Y, Sun K. Adv. Synth. Catal. 2021; 363: 5235 8d Mustafa A, Siddiqui S, Umar Khan M, Qasem Ali AA, Siddiqui ZN. ChemistrySelect 2021; 6: 8611 8e Li M.-M, Chen X, Deng Y, Lu J. RSC Adv. 2021; 11: 38060 9 Zeng L, Guo X.-Q, Yang Z.-J, Gan Y, Chen L.-M, Kang T.-R. Tetrahedron Lett. 2019; 60: 150943 10 Chen L.-M, Zhao J, Xia A.-J, Guo X.-Q, Gan Y, Zhou C, Yang Z.-J, Yang J, Kang T.-R. Org. Biomol. Chem. 2019; 17: 8561 11 Yang J.-G, Xu L.-Z, Huang L, Gao J.-R, Liu M.-C, Pan F.-Y, Chen D.-B. Chin. Chem. Lett. 2016; 27: 340 12a For a recent review on phosphazene base catalyzed reactions, see: Puleo TR, Sujansky SJ, Wright SE, Bandar JS. Chem. Eur. J. 2021; 27: 4216 12b Shigeno M, Nakamura R, Hayashi K, Nozawa-Kumada K, Kondo Y. Org. Lett. 2019; 21: 6695 12c Shigeno M, Hayashi K, Nozawa-Kumada K, Kondo Y. Chem. Eur. J. 2019; 25: 6077 12d Shigeno M, Hayashi K, Nozawa-Kumada K, Kondo Y. Org. Lett. 2019; 21: 5505 12e Shigeno M, Hayashi K, Nozawa-Kumada K, Kondo Y. Org. Lett. 2020; 22: 9107 12f Shigeno M, Hayashi K, Korenaga T, Nozawa-Kumada K, Kondo Y. Org. Chem. Front. 2022; 9: 3656 12g Shigeno M, Shishido Y, Hayashi K, Nozawa-Kumada K, Kondo Y. Eur. J. Org. Chem. 2021; 3932 13 Wang X, Li Z, Cao S, Rao H. Adv. Synth. Catal. 2016; 358: 2059 14 Walia PK, Sharma M, Kumar M, Bhalla V. RSC Adv. 2019; 9: 36198 15 Experimental Procedure for the One-Pot Synthesis of Pyrazoloindolone 5a A round-bottomed flask (10 mL) fitted with a magnetic stir bar and nitrogen inlet was charged with cinnamaldehyDe (26.2 mg, 0.20 mmol) and MeOH (0.40 mL) at rt. Then TsNHNH2 (37.2 mg, 0.20 mmol) was added, and the mixture was stirred at rt for 3 h. During this time TLC analysis indicated complete conversion. Then, MeOH was evaporated, the residue was dissolved in dry DMSO (0.40 mL), and Cs2CO3 (81.5 mg, 0.25 mmol) was added under nitrogen atmosphere. The resulting mixture was placed in a pre-heated oil bath at 110 °C and stirred for 15 min. Then, 2-fluorobenzaldehyde 3a (24.8 mg, 0.20 mmol) and Cs2CO3 (146.6 mg, 0.45 mmol) were added, and the reaction mixture was stirred at 110 °C for 5 h. Then, the reaction mixture was purged with oxygen and heated at 130 °C under oxygen atmosphere (balloon) for 10 h. After cooling to rt, the reaction mixture was diluted with ethyl acetate (25 mL), extracted with brine (3 × 10 mL), dried over Na2SO4, and evaporated. The crude product was purified by silica gel column chromatography using 5% ethyl acetate in hexanes as eluent to obtain pyrazoloindolone 5a (32.1 mg, 65% yield) as a yellow-brown solid; mp 150–152 °C; Rf = 0.75 (0.5:9.5 ethyl acetate/hexane); purified using 2% ethyl acetate in hexanes as eluent. 1H NMR (500 MHz, CDCl3): δ = 7.76 (d, J = 6.5 Hz, 2 H), 7.53 (d, J = 6.5 Hz, 1 H), 7.45 (apt, J = 7.5 Hz, 1 H), 7.40–7.34 (m, 3 H), 7.29 (apt, J = 8.0 Hz, 1 H), 7.12 (apt, J = 8.0 Hz, 1 H), 6.86 (s, 1 H). 13C{1H} NMR (126 MHz, CDCl3): δ = 179.5, 157.9, 144.0, 139.7, 135.6, 132.0, 128.8, 128.7, 128.0, 126.3, 125.6, 124.9, 110.7, 103.3. HRMS (ESI-TOF): m/z calcd for C16H11N2O [M + H]+: 247.0871; found: 247.0842. Zusatzmaterial Zusatzmaterial Supporting Information
