Metal- and Solvent-Free Synthesis of m-Terphenyls by an Iodine-Catalyzed Tandem Formal [3+3]-Cycloaddition/Oxidation

Thangavel Pavithra; Gnanaoli Karthiyayini; Subbiah Nagarajan; Vellaisamy Sridharan; C. Uma Maheswari

doi:10.1055/a-1903-5174

Synlett, Table of Contents

Synlett 2023; 34(07): 807-814
DOI: 10.1055/a-1903-5174

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Chemical Synthesis and Catalysis in India

Metal- and Solvent-Free Synthesis of m-Terphenyls by an Iodine-Catalyzed Tandem Formal [3+3]-Cycloaddition/Oxidation

Thangavel Pavithra

^aDepartment of Chemistry, School of Chemical and Biotechnology, SASTRA Deemed University, Thanjavur-613401, India

,

Gnanaoli Karthiyayini

^aDepartment of Chemistry, School of Chemical and Biotechnology, SASTRA Deemed University, Thanjavur-613401, India

,

Subbiah Nagarajan

^bDepartment of Chemistry, National Institute of Technology-Warangal, Warangal-506004, India

,

Vellaisamy Sridharan

^cDepartment of Chemistry and Chemical Sciences, Central University of Jammu, Rahya-Suchani (Bagla), District-Samba, Jammu-181143, Jammu and Kashmir, India

,

C. Uma Maheswari∗

^aDepartment of Chemistry, School of Chemical and Biotechnology, SASTRA Deemed University, Thanjavur-613401, India

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Abstract

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Abstract

A tandem formal [3+3]-cycloaddition/oxidation between chalcones and β-enamine esters, employing iodine as a catalyst, was developed for the construction of various substituted m-terphenyls. A wide range of chalcones and β-enamine esters were tested under metal- and solvent-free conditions for the synthesis of substituted m-terphenyls in good to excellent yields in the presence of sulfur as an oxidant. This reaction proceeds with the formation of four new bonds and one new ring, with a high atom economy.

Key words

terphenyls - chalcones - enamine esters - cycloaddition - iodine catalysis - oxidation

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References and Notes

1a Liu J.-K. Chem. Rev. 2006; 106: 2209
1b Electronic Materials: The Oligomer Approach . Müllen K, Wegner G. Wiley-VCH; Weinhein: 1988
1c Cook TR, Zheng Y.-R, Stang PJ. Chem. Rev. 2013; 113: 734

2 Todd MH, Balasubramanian S, Abell C. Tetrahedron Lett. 1997; 38: 6781
3 Córsico EF, Rossi RA. Synlett 2000; 230

4a Udayakumar BS, Schuster GB. J. Org. Chem. 1992; 57: 348
4b Wright RS, Vinod TK. Tetrahedron Lett. 2003; 44: 7129
4c Liao H.-R, Lin Y.-J, Chou Y.-M, Luo F.-T, Wang B.-C. J. Lumin. 2008; 128: 1373

5a Yashima E, Maeda K, Furusho Y. Acc. Chem. Res. 2008; 41: 1166
5b Furusho Y, Yashima E. Chem. Rec. 2007; 7: 1
5c Goto H, Furusho Y, Miwa K, Yashima E. J. Am. Chem. Soc. 2009; 131: 4710
5d Yamada H, Wu Z.-Q, Furusho Y, Yashima E. J. Am. Chem. Soc. 2012; 134: 9506

6 Yen Y.-S, Chen W.-T, Hsu C.-Y, Chou HH, Lin JT, Yeh M.-CP. Org. Lett. 2011; 13: 4930

7a Glombitza K.-W, Rauwald H.-W, Eckhard G. Phytochemistry 1975; 14: 1403
7b Kouno I, Hashimoto A, Kawano N, Yang C.-S. Chem. Pharm. Bull. 1989; 37: 1291
7c Kouno I, Morisaki T, Hara Y, Yang C.-S. Chem. Pharm. Bull. 1991; 39: 2606
7d Kouno I, Iwamoto C, Kameda Y, Tanaka T, Yang C.-S. Chem. Pharm. Bull. 1994; 42: 112
7e Kohno H, Takaba K, Fukai T, Nomura T. Heterocycles 1987; 26: 759
7f Kikuchi H, Matsuo Y, Katou Y, Kubohara Y, Oshima Y. Tetrahedron 2012; 68: 8884

8a Sawayama Y, Tsujimoto T, Sugino K, Nishikawa T, Isobe M, Kawagishi H. Biosci., Biotechnol., Biochem. 2006; 70: 2998
8b Cali V, Spatafora C, Tringali C. Stud. Nat. Prod. Chem. 2003; 29: 263

9 Patrick DA, Ismail MA, Arafa RK, Wenzler T, Zhu X, Pandharkar T, Kilgore Jones S, Werbovetz KA, Brun R, Boykin DW, Tidwell RR. J. Med. Chem. 2013; 56: 5473
10 Rajakumar P, Padmanabhan R, Rajesh N. Bioorg. Med. Chem. Lett. 2012; 22: 3770
11 Samshuddin S, Narayana B, Sarojini BK, Shetty DN, Kumari NS. Int. J. Med. Chem. 2012; 530392
12 Bauer JD, Foster MS, Hugdahl JD, Burns KL, May SW, Pollock SH, Cutler HG, Cutler S. J. 2007; 16: 119

13a Twamley B, Haubrich ST, Power PP. Adv. Organomet. Chem. 1999; 44: 1
13b Clyburne JA. C, McMullen N. Coord. Chem. Rev. 2000; 210: 73
13c Kays DL, Cowley AR. Chem. Commun. 2007; 1053
13d Rivard E, Power PP. Inorg. Chem. 2007; 46: 10047
13e Kays DL. Organomet. Chem. 2010; 36: 56
13f Kays DL. Dalton Trans. 2011; 40: 769
13g Kays DL. Chem. Soc. Rev. 2016; 45: 1004
13h Veinot AJ, Todd AD. K, Masuda JD. A. Angew. Chem. Int. Ed. 2017; 56: 11615

14a Grimsdale AC, Müllen K. Angew. Chem. Int. Ed. 2005; 44: 5592
14b Kissel P, Breitler S, Reinmüller V, Lanz P, Federer L, Schlüter AD, Sakamoto J. Eur. J. Org. Chem. 2009; 2009: 2953
14c Bhalla V, Tejpal R, Kumar M, Sethi A. Inorg. Chem. 2009; 48: 11677
14d Wu C.-A, Chou H.-H, Shih C.-H, Wu F.-I, Cheng C.-H, Huang H.-L, Chao T.-C, Tseng M.-R. J. Mater. Chem. 2012; 22: 17792
14e Karastatiris P, Mikroyannidis JA, Spiliopoulos IK, Fakis M, Persephonis P. J. Polym. Sci., Part A: Polym. Chem. 2004; 42: 2214
14f Okazawa Y, Kondo K, Akita M, Yoshizawa M. Chem. Sci. 2015; 6: 5059
14g Riddle JA, Bollinger JC, Lee D. Angew. Chem. Int. Ed. 2005; 44: 6689
14h Lüning U, Baumgartner H, Manthey C, Meynhardt B. J. Org. Chem. 1996; 61: 7922

15a Morgan BP, Gilliard RJ. Jr, Loungani RS, Smith RC. Macromol. Rapid Commun. 2009; 30: 1399
15b Annan KO, Scherf U, Mullen K. Synth. Met. 1999; 99: 9
15c Vinod TK, Hart H. J. Am. Chem. Soc. 1990; 112: 3250
15d Grewal RS, Hart H, Vinod TK. J. Org. Chem. 1992; 57: 2721
15e Vinod TK, Hart H. J. Org. Chem. 1991; 56: 5630
15f Vinod T, Hart H. J. Org. Chem. 1990; 55: 881

16a Adrio LA, Antelo Miguez JM, Hii KK. Org. Prep. Proced. Int. 2009; 41: 331
16b Du C.-JF, Hart H, Ng K.-KD. J. Org. Chem. 1986; 51: 3162
16c Saednya A, Hart H. Synthesis 1996; 1455
16d Hino S, Olmstead MM, Fettinger JC, Power PP. J. Organomet. Chem. 2005; 690: 1638
16e Chang M.-Y, Lee T.-W, Lin S.-Y. Tetrahedron 2013; 69: 228
16f Rottländer M, Knochel P. J. Org. Chem. 1998; 63: 203
16g Rashidzadeh B, Jafarpour F, Saednya A. ARKIVOC 2008; (xvii): 167
16h Antelo Míguez JM, Adrio LA, Sousa-Pedrares A, Vila JM, Hii KK. J. Org. Chem. 2007; 72: 7771

17a Poudel TN, Tamargo RJ. I, Cai H, Lee YR. Asian J. Org. Chem. 2018; 7: 985
17b Fernandes RA, Kumari A, Pathare RS. Synlett 2020; 31: 403
17c Xia Y, Huang H, Zhang F, Deng G.-J. Org. Lett. 2019; 21: 7489
17d Yang S, Lu D, Huo H, Luo F, Gong Y. Org. Lett. 2018; 20: 6943
17e Hilt G, Danz M. Synthesis 2008; 2257

18a Gopi E, Namboothiri IN. N. J. Org. Chem. 2014; 79: 7468
18b Chang M.-Y, Chan C.-K, Lin S.-Y, Wu M.-H. Tetrahedron 2013; 69: 9616
18c Yaragorla S, Dada R. ACS Omega 2017; 2: 4859
18d Rocchi D, González JF, Gómez-Carpintero J, González-Ruiz V, Martín MA, Sridharan V, Menéndez JC. ACS Comb. Sci. 2018; 20: 722
18e Xing M.-M, Xu H, Hou L.-F, Gao J.-R, Li Y.-J. RSC Adv. 2016; 6: 10943

19a Pavithra T, Devi ES, Nagarajan S, Sridharan V, Uma Maheswari C. Eur. J. Org. Chem. 2019; 2019: 6884
19b Pavithra T, Devi ES, Nagarajan S, Sridharan V, Uma Maheswari C. ChemistrySelect 2021; 6: 3548

20a Nguyen TB, Retailleau P. J. Org. Chem. 2019; 84: 5907
20b Shibahara F, Sugiura R, Yamaguchi E, Kitagawa A, Murai T. J. Org. Chem. 2009; 74: 3566
20c Wang Z, Chen X, Xie H, Wang D, Huang H, Deng G.-J. Org. Lett. 2018; 20: 5470

21a Nguyen TB, Nguyen LA, Retailleau P. Org. Lett. 2019; 21: 6570
21b Wang Z, Li C, Huang H, Deng G.-J. J. Org. Chem. 2020; 85: 9415
21c Nguyen TB, Retailleau P. Adv. Synth. Catal. 2019; 361: 3588

22a von der Heiden D, Bozkus S, Klussmann M, Breugst M. J. Org. Chem. 2017; 82: 4037
22b Revannath L, Sutar Sutar, Huber SM. ACS Catal. 2019; 9: 9622

23a Finkbeiner P, Nachtsheim BJ. Synthesis 2013; 45: 979
23b Zhang Z, Liu Q. Huaxue Jinzhan 2006; 18: 270
23c Banerjee AK, Vera W, Mora H, Laya MS, Bedoya L, Cabrera EV. J. Sci. Ind. Res. 2006; 65: 299
23d Wang S.-Y. Synlett 2004; 2642
23e Zhang J, Wu X, Gao Q, Geng X, Zhao P, Wu Y.-D, Wu A. Org. Lett. 2017; 19: 408
23f Naresh G, Kant R, Narender T. J. Org. Chem. 2014; 79: 3821
23g Lv Z, Liu J, Wei W, Wu J, Yu W, Chang J. Adv. Synth. Catal. 2016; 358: 2759
23h Cui H, Liu X, Wei W, Yang D, He C, Zhang T, Wang H. J. Org. Chem. 2016; 81: 2252
23i Jadhav PM, Rode AB, Kótai L, Pawar RP, Tekale SU. New J. Chem. 2021; 45: 16389

24a Ge W, Zhu X, Wei Y. RSC Adv. 2013; 3: 10817
24b Koenig JJ, Arndt T, Gildemeister N, Neudörfl J.-M, Breugst M. J. Org. Chem. 2019; 84: 7587
24c Silva LF. Jr, Quintiliano SA. Tetrahedron Lett. 2009; 50: 2256
24d Yadav JS, Reddy BV. S, Kumar GG. K. S. N, Swamy T. Tetrahedron Lett. 2007; 48: 2205
24e Yadav JS, Reddy BV. S, Krishna VH, Swamy T, Kumar GG. K. S. Can. J. Chem. 2007; 85: 412
24f Yadav JS, Reddy BV. S, Chaya DN, Kumar GG. K. S. N, Aravind S, Kunwar AC, Madavi C. Tetrahedron Lett. 2008; 49: 3330
24g Knight DW. Prog. Heterocycl. Chem. 2002; 14: 19
24h Sun J, Dong Y, Cao L, Wang X, Wang S, Hu Y. J. Org. Chem. 2004; 69: 8932
24i Bosco JW. J, Agrahari A, Saikia AK. Tetrahedron Lett. 2006; 47: 4065
24j Marsili LA, Pergomet JL, Gandon V, Riveira MJ. Org. Lett. 2018; 20: 7298
24k Aegurla B, Jarwal N, Peddinti RK. Org. Biomol. Chem. 2020; 18: 6100

25 Zhang H, Cai Q, Ma D. J. Org. Chem. 2005; 70: 5164
26 Qian Q, Tan Y, Zhao B, Feng T, Shen Q, Yao Y. Org. Lett. 2014, 16 4516. m-Terphenyls 3a–u; General Procedure A mixture of the appropriate α,β-unsaturated carbonyl compound (1.0 mmol) and β-enaminone (1.5 mmol) with I₂ (10 mol%) and elemental sulfur (1.0 equiv) in a reaction vial was stirred at 120 °C until the reaction was complete (TLC). H₂O was then added and the mixture was extracted with EtOAc. The extracts were washed with brine, dried (Na₂SO₄), and concentrated under vacuum to give a crude product that was purified by column chromatography [silica gel, hexane–EtOAc (95:5)]. Ethyl 5′-(Butylamino)-4-methoxy-[1,1′:3′,1′′-terphenyl]-4′-carboxylate (3b) Yellow solid; yield: 330 mg (82%); mp 112–115 °C. ¹H NMR (600 MHz, CDCl₃): δ = 7.62–7.60 (m, 2 H), 7.44–7.41 (m, 2 H), 7.37–7.34 (m, 1 H), 7.26–7.25 (m, 1 H), 7.24–7.24 (m, 1 H), 6.91–6.89 (m, 2 H), 6.82–6.79 (m, 2 H), 6.38 (s, 1 H), 3.91 (q, J = 7.2 Hz, 2 H), 3.83 (s, 3 H), 3.23 (q, J = 7.2 Hz, 2 H), 1.69 (quin, J = 7.2 Hz, 2 H), 1.47 (sextet, J = 7.2 Hz, 2 H), 0.97 (t, J = 7.2 Hz, 3 H), 0.77 (t, J = 7.2 Hz, 3 H). ¹³C NMR (150 MHz, CDCl₃): δ = 170.2, 158.8, 149.5, 144.8, 144.5, 141.2, 136.4, 129.2, 128.8, 127.9, 127.4, 117.5, 113.5, 112.3, 108.5, 60.4, 55.5, 43.3, 31.5, 20.4, 14.0, 13.5. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₆H₃₀NO₃: 404.21; found: 404.21. Ethyl 3-(Butylamino)-5-(1-naphthyl)biphenyl-2-carboxylate (3c) Yellow solid; yield: 313 mg (74%); mp 71–74 °C. ¹H NMR (600 MHz, CDCl₃): δ = 8.07 (s, 1 H), 7.90–7.85 (m, 3 H), 7.76 (dd, J = 1.8, 7.2 Hz, 1 H), 7.50–7.48 (m, 2 H), 7.37–7.32 (m, 5 H), 6.98 (d, J = 1.2 Hz, 1 H), 6.95 (d, J = 1.2 Hz, 1 H), 6.57 (br s, 1 H), 3.88 (q, J = 7.2 Hz, 2 H), 3.29 (q, J = 7.2 Hz, 2 H), 1.72 (quin, J = 7.2 Hz, 2 H), 1.50 (sextet, J = 7.2 Hz, 2 H), 0.989 (t, J = 7.2 Hz, 3 H), 0.699 (t, J = 7.2 Hz, 3 H). ¹³C NMR (150 MHz, CDCl₃): δ = 170.1, 149.9, 145.3, 144.8, 144.1, 138.4, 133.7, 133.1, 128.5, 128.4, 128.1, 128.0, 127.8, 126.8, 126.5, 126.2, 125.6, 117.7, 111.9, 109.0, 60.4, 43.3, 31.5, 20.5, 14.1, 13.2. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₉H₃₀NO₂: 424.21; found: 424.21

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