Synthesis of Benzo-Fused Cyclic Compounds via Rhodium-Catalyzed Decarboxylative Coupling of Aromatic Carboxylic Acids with Alkynes

Abstract

The decarboxylative coupling of diversely substituted benzoic acids with internal alkynes proceeds smoothly in the presence of a [RhCl(cod)]₂/1,2,3,4-tetraphenyl-1,3-cyclopentadiene catalyst system to selectively produce highly substituted naphthalene derivatives. The catalyst system is applicable to constructing anthracene and benzo­[c]thiophene frameworks through reactions of naphthoic and thiophene-2-carboxylic acids, respectively.

Key words

C–H functionalization - carboxylic acids - decarboxylative coupling - homologation - rhodium catalysis

Publication History

Received: 17 February 2021

Accepted after revision: 08 March 2021

Accepted Manuscript online:
08 March 2021

Article published online:
01 April 2021

• References


For representative reviews, see:
• 1a Wei Y, Hu P, Zhang M, Su W. Chem. Rev. 2017; 117: 8864
• 1b Font M, Quibell JM, Perry GJ. P, Larrosa I. Chem. Commun. 2017; 53: 5584
• 1c Drapeau MP, Gooßen LJ. Chem. Eur. J. 2016; 23: 18654
• 1d Satoh T, Miura M. Synthesis 2010; 3395

For pioneering work, see:
• 2a Murai S, Kakiuchi F, Sekine S, Tanaka Y, Kamatani A, Sonoda M, Chatani N. Nature 1993; 366: 529

See also selected reviews on C–H functionalization:
• 2b Sambiagio C, Schönbauer D, Blieck R, Dao-Huy T, Pototschnig G, Schaaf P, Wiesinger T, Farooq Zia M, Wencel-Delord J, Besset T, Maes BU. W, Schnürch M. Chem. Soc. Rev. 2018; 47: 6603
• 2c Gulías M, Mascareñas JL. Angew. Chem. Int. Ed. 2016; 55: 11000
• 2d Chen Z, Wang B, Zhang J, Yu W, Liu Z, Zhang Y. Org. Chem. Front. 2015; 2: 1107
• 2e Song G, Li X. Acc. Chem. Res. 2015; 48: 1007
• 2f Ye J, Lautens M. Nat. Chem. 2015; 7: 863
• 2g Miura M, Satoh T, Hirano K. Bull. Chem. Soc. Jpn. 2014; 87: 751
• 2h De Sarkar S, Liu W, Kozhushkov SI, Ackermann L. Adv. Synth. Catal. 2014; 356: 1461
• 2i Wencel-Delord J, Glorius F. Nat. Chem. 2013; 5: 369
• 2j Colby DA, Tsai AS, Bergman RG, Ellman JA. Acc. Chem. Res. 2012; 45: 814
• 2k Engle KM, Mei T.-S, Wasa M, Yu J.-Q. Acc. Chem. Res. 2012; 45: 788
• 2l Cho SH, Kim JY, Kwak J, Chang S. Chem. Soc. Rev. 2011; 40: 5068
• 2m Giri R, Shi B.-F, Engle KM, Maugel N, Yu J.-Q. Chem. Soc. Rev. 2009; 38: 3242
• 3a Unoh Y, Hirano K, Satoh T, Miura M. Tetrahedron 2013; 69: 4454
• 3b Shimizu M, Hirano K, Satoh T, Miura M. J. Org. Chem. 2009; 74: 3478
• 3c Ueura K, Satoh T, Miura M. Org. Lett. 2007; 9: 1407
• 4a Hirosawa K, Usuki Y, Satoh T. Adv. Synth. Catal. 2019; 361: 5253
• 4b Ueura K, Satoh T, Miura M. J. Org. Chem. 2007; 72: 5362

For homologation reactions of readily available mono-substituted aromatic substrates, see:
• 5a Wang H, Wang Y, Yang H, Tan C, Jiang Y, Zhao Y, Fu H. Adv. Synth. Catal. 2015; 357: 489
• 5b Fukutani T, Hirano K, Satoh T, Miura M. J. Org. Chem. 2011; 76: 2867
• 5c Uto T, Shimizu M, Ueura K, Tsurugi H, Satoh T, Miura M. J. Org. Chem. 2008; 73: 298
• 5d Yasukawa T, Satoh T, Miura M, Nomura M. J. Am. Chem. Soc. 2002; 124: 12680
• 5e Kawasaki S, Satoh T, Miura M, Nomura M. J. Org. Chem. 2003; 68: 6836
• 5f Wu G, Rheingold AL, Feib SL, Heck RF. Organometallics 1987; 6: 1941
• 5g Sakakibara T, Tanaka Y, Yamasaki T.-I. Chem. Lett. 1986; 797
• 6a Honjo Y, Shibata Y, Tanaka K. Chem. Eur. J. 2019; 25: 9427
• 6b Honjo Y, Shibata Y, Kudo E, Namba T, Masutomi K, Tanaka K. Chem. Eur. J. 2018; 24: 317
• 7a Molotkov AP, Arsenov MA, Kapustin DA, Muratov DV, Shepel’ NE, Fedorov YV, Smol’yakov AF, Knyazeva EI, Lypenko DA, Dmitriev AV, Aleksandrov AE, Maltsev EI, Loginov DA. ChemPlusChem 2020; 85: 334
• 7b Datsenko VP, Nelyubina YV, Smol’yakov AF, Loginov DA. J. Organomet. Chem. 2018; 874: 7
• 7c Loginov DA, Konoplev VE. J. Organomet. Chem. 2018; 867: 14
• 7d Loginov DA, Belova AO, Kudinov AR. Russ. Chem. Bull. 2014; 63: 983

The catalyst system of [RhCl(cod)]₂/C₅H₂Ph₄ has been employed for various dehydrogenative couplings, see:
• 8a Shimizu M, Tsurugi H, Satoh T, Miura M. Chem. Asian J. 2008; 3: 881
• 8b Umeda N, Tsurugi H, Satoh T, Miura M. Angew. Chem. Int. Ed. 2008; 47: 4019
• 8c Mochida S, Shimizu M, Hirano K, Satoh T, Miura M. Chem. Asian J. 2010; 5: 847
• 9 In contrast, C₅H₂Ph₄ is known to readily coordinate to rhodium, see: Davies DL, Ellul CE, Singh K. J. Organomet. Chem. 2019; 879: 151

For example, see:
• 10a Chávez-González M, Rodríguez-Durán LV, Balagurusamy N, Prado-Barragán A, Rodríguez R, Contreras JC, Aguilar CN. Food Bioprocess Technol. 2012; 5: 445
• 10b Moodley B, Mulholland DA, Brookes HC. Water SA 2012; 38: 1
• 10c van Haveren J, Scott EL, Sanders J. Biofuels Bioprod. Bioref. 2008; 2: 41
• 10d Xu Y, Hanna MA, Isom L. Open Agric. J. 2008; 2: 54
• 10e Kambourakis S, Draths KM, Frost JW. J. Am. Chem. Soc. 2000; 122: 9042
• 11 A similar regioselective annulation has been observed in the ruthenium-catalyzed 1:1 coupling of 1n with alkynes, see: Chinnagolla RK, Jeganmohan M. Chem. Commun. 2012; 48: 2030
• 12 For related selective anthracene construction from 2-naphthaleneboronic acids, see ref. 5b.
• 13 For the related synthesis of benzo[c]thiophenes from thiophene-2-carbamides, see: Fukuzumi K, Unoh Y, Nishii Y, Satoh T, Hirano K, Miura M. J. Org. Chem. 2016; 81: 2474
• 14a Novák Z, Nemes P, Kotschy A. Org. Lett. 2004; 6: 4917
• 14b Moon J, Jang M, Lee S. J. Org. Chem. 2008; 74: 1403
• 14c Hein SJ, Arslan H, Keresztes I, Dichtel WR. Org. Lett. 2014; 16: 4416
• 15 Peng S, Sun Z, Zhu H, Chen N, Sun X, Gong X, Wang J, Wang L. Org. Lett. 2020; 22: 3200
• 16 Wu YT, Huang K.-H, Shin C.-C, Wu T.-C. Chem. Eur. J. 2008; 14: 6697