Heteroatom-Embedding Annulative π-Extension (Hetero-APEX) Reactions: An Overview

Abstract

Heteroatom-embedded polycyclic aromatic compounds (hetero-PACs) are a class of organic compounds contributing to a variety of research fields such as materials science, chemical biology, and so on. For applications using hetero-PACs, efficient preparation of hetero-PACs is essential. In particular, reactions transforming unfunctionalized aromatic compounds into hetero-PACs using appropriate heteroatom-containing aromatic compounds (π-extending agents) represent the most ideal way to prepare hetero-PACs. In this review, such heteroatom-embedding annulative π-extension (hetero-APEX) reactions, including their reaction mechanisms and scope of substrates, are described.

1 Introduction

2 Oxa-APEX Reactions

3 Aza-APEX Reactions

4 Thia-APEX Reactions

5 Conclusion and Outlook

Key words

annulative π-extension - polycyclic aromatic compounds - annulation - heteroaromatics - π-extended compounds - heteroles

Publication History

Received: 17 August 2023

Accepted after revision: 06 September 2023

Accepted Manuscript online:
06 September 2023

Article published online:
18 October 2023

• References

• 1a Stępień M, Gońka E, Żyła M, Sprutta N. Chem. Rev. 2017; 117: 3479
• 1b Borissov A, Maurya YK, Moshniaha L, Wong W.-S, Żyła-Karwowska M, Stępień M. Chem. Rev. 2022; 122: 565
• 1c Li H, Shi W, Song J, Jang H.-J, Dailey J, Yu J, Katz HE. Chem. Rev. 2019; 119: 3
• 1d Karak P, Rana SS, Choudhury J. Chem. Commun. 2022; 58: 133
• 1e Wang C, Dong H, Hu W, Liu Y, Zhu D. Chem. Rev. 2012; 112: 2208
• 1f Janosik T, Rannug A, Rannug U, Wahlström N, Slatt J, Bergman J. Chem. Rev. 2018; 118: 9058
• 1g Hirai M, Tanaka N, Sakai M, Yamaguchi S. Chem. Rev. 2019; 119: 8291
• 1h Dhbaibi K, Favereau L, Crassous J. Chem. Rev. 2019; 119: 884
• 1i Wöhrle T, Wurzbach I, Kirres J, Kostidou A, Kapernaum N, Litterscheidt J, Haenle JC, Staffeld P, Baro A, Giesselmann F, Laschat S. Chem. Rev. 2016; 116: 1139
• 1j Cai Z, Awais MA, Zhang N, Yu L. Chem 2018; 4: 2538
• 1k Anthony JE. Chem. Rev. 2006; 106: 5028
• 2a Terrones H, Lv R, Terrones M, Dresselhaus MS. Rep. Prog. Phys. 2012; 75: 062501
• 2b Szűcs R, Bouit P.-A, Nyulászi L, Hissler M. ChemPhysChem 2017; 18: 2618
• 2c Jeong E.-J, Kim Y.-K, Park J.-H, Lee E.-Y, Hwang S.-H. US 20150349275A1, 2015
• 2d Nakayama K, Hashimoto Y, Sasabe H, Pu Y.-J, Yokoyama M, Kido J. Jpn. J. Appl. Phys. 2010; 49: 01AB11
• 2e Yamaguchi AD, Chepiga KM, Yamaguchi J, Itami K, Davies HM. L. J. Am. Chem. Soc. 2015; 137: 644
• 2f Ma Y, Sun Y, Liu Y, Gao J, Chen S, Sun X, Qiu W, Yu G, Cui G, Hu W, Zhu D. J. Mater. Chem. 2005; 15: 4894
• 2g Bazzini C, Brovelli S, Caronna T, Gambarotti C, Giannone M, Macchi P, Meinardi F, Mele A, Panzeri W, Recupero F, Sironi A, Tubino R. Eur. J. Org. Chem. 2005; 1247
• 2h Xiao L, Lan H, Kido J. Chem. Lett. 2007; 36: 802
• 2i Cheng C.-H, Wu J.-L, Liao C.-Y. US 8753756B2, 2014
• 2j Mamada M, Minamiki T, Katagiri H, Tokito S. Org. Lett. 2012; 14: 4062
• 2k Tanaka K, Iwama Y, Kishimoto M, Ohtsuka N, Hoshino Y, Honda K. Org. Lett. 2020; 22: 5207
• 2l Li M, Xie W, Cai X, Peng X, Liu K, Gu Q, Zhou J, Qiu W, Chen Z, Gan Y, Su S.-J. Angew. Chem. Int. Ed. 2022; 61: e202209343
• 2m Tsuji H, Nakamura E. Acc. Chem. Res. 2017; 50: 396
• 2n Chen X, Yan L, Liu Y, Yang Y, You J. Chem. Commun. 2020; 56: 15080
• 3a Marco-Contelles J, Pérez-Mayoral E, Samadi A, Carreiras M. dC, Soriano E. Chem. Rev. 2009; 109: 2652
• 3b Sun Y.-X, Wang X.-G, Shen G.-D, Yang T, Yang Y.-H, Li J, Yang M.-Y, Sun H.-M, Wei J.-F. Adv. Synth. Catal. 2020; 362: 1651
• 3c Goujon A, Rocard L, Cauchy T, Hudhomme P. J. Org. Chem. 2020; 85: 7218
• 3d Strekowski L, Czarny A, Lee H. J. Fluorine Chem. 2000; 104: 281
• 3e Tsvelikhovsky D, Buchwald SL. J. Am. Chem. Soc. 2010; 132: 14048
• 3f Ye X, Xu B, Sun J, Dai L, Shao Y, Zhang Y, Chen J. J. Org. Chem. 2020; 85: 13004
• 3g Wang T.-J, Chen W.-W, Lia Y, Xu M.-H. Org. Biomol. Chem. 2015; 13: 6580
• 3h Pang X, Lou Z, Li M, Wen L, Chen C. Eur. J. Org. Chem. 2015; 3361
• 3i Guo H.-M, Mao R.-Z, Wang Q.-T, Niu H.-Y, Xie M.-S, Qu G.-R. Org. Lett. 2013; 15: 5460

Examples of construction of pyrylium/thiopyrylium structures:
• 4a Kharchenko VG, Kleimenova VI, Yakoreva AR. Chem. Heterocycl. Compd. 1970; 6: 834
• 4b Berényi S, Tóth M, Gyulai S, Szilágyi L. Heterocycles 2002; 57: 135
• 4c Wu D, Pisula W, Haberecht MC, Feng X, Müllen K. Org. Lett. 2009; 11: 5686
• 4d Nagahora N, Kushida T, Shioji K, Okuma K. Organometallics 2019; 38: 1800
• 4e Tanaka K, Kishimoto M, Sukekawa M, Hoshino Y, Honda K. Tetrahedron Lett. 2018; 59: 3361
• 4f Shen G.-B, Xia K, Li X.-T, Li J.-L, Fu Y.-H, Yuan L, Zhu X.-Q. J. Phys. Chem. A 2016; 120: 1779
• 4g Shenbor MI, Azarov AS. Khim. Getero. Soedin. 1979; 29
• 4h Rao KP, Kusamoto T, Toshimitsu F, Inayoshi K, Kume S, Sakamoto R, Nishihara H. J. Am. Chem. Soc. 2010; 132: 12472
• 4i Wehrmann CM, Charlton RT, Chen MS. J. Am. Chem. Soc. 2019; 141: 3240
• 4j Spiliopoulos IK, Mikroyannidis JA. Macromolecules 2002; 35: 7254
• 5 Lv B, Xiao J, Zhou J, Zhang X, Duan J, Su W, Zhao J. ACS Appl. Mater. Interfaces 2016; 8: 18998
• 6 Saint-Ruf G, Buu-Hoï NP, Jacquignon P. J. Chem. Soc. 1958; 1773
• 7 Zhang S, Qiao X, Chen Y, Wang Y, Edkins RM, Liu Z, Li H, Fang Q. Org. Lett. 2014; 16: 342
• 8a Mackey K, Jones DJ, Pardo LM, McGlacken GP. Eur. J. Org. Chem. 2021; 495
• 8b Đorđević L, Milano D, Demitri N, Bonifazi D. Org. Lett. 2020; 22: 4283

Other examples of constructing heteroaromatic rings:
• 9a Waley MW, Gorindachari TR. Org. React. 1951; 6: 74
• 9b Imran M, Wehrmann CM, Chen MS. J. Am. Chem. Soc. 2020; 142: 38
• 9c Greßies S, Ito M, Sakai M, Osaki H, Kim JH, Gensch T, Daniliuc C, Ando N, Yamaguchi S, Glorius F. Chem. Eur. J. 2021; 27: 2753
• 9d Larock RC, Yum EK, Refvik MD. J. Org. Chem. 1998; 63: 7652
• 9e Masuya Y, Tobisu M, Chatani N. Org. Lett. 2016; 18: 4312
• 9f Zeng W, Wu W, Jiang H, Huang L, Sun Y, Chen Z, Li X. Chem. Commun. 2013; 49: 6611
• 9g Wang S, Lv B, Cui Q, Ma X, Ba X, Xiao J. Chem. Eur. J. 2015; 21: 14791
• 9h Yue D, Larock RC. J. Org. Chem. 2002; 67: 1905
• 9i Meng L, Fujikawa T, Kuwayama M, Segawa Y, Itami K. J. Am. Chem. Soc. 2016; 138: 10351
• 9j Song T, Han Y, Jin P, Li X, Song Y, Xiao J. J. Mater. Chem. C 2019; 7: 6344
• 9k Miletić T, Fermi A, Orfanos I, Avramopoulos A, De Leo F, Demitri N, Bergamini G, Ceroni P, Papadopoulos MG, Couris S, Bonifazi D. Chem. Eur. J. 2017; 23: 2363
• 9l Saha M, Bao Y.-H, Zhou CA. Chem. Lett. 2018; 47: 1383
• 9m Ma Y, Shi Z, Zhang A, Li J, Wei X, Jiang T, Li Y, Wang X. Dyes Pigm. 2016; 135: 41
• 10a Ito H, Ozaki K, Itami K. Angew. Chem. Int. Ed. 2017; 56: 11144
• 10b Ito H, Segawa Y, Murakami K, Itami K. J. Am. Chem. Soc. 2019; 141: 3

Representative examples of APEX reaction of PAH and heteroaromatics:
• 11a Ozaki K, Zhang H, Ito H, Lei A, Itami K. Chem. Sci. 2013; 4: 3416
• 11b Ozaki K, Kawasumi K, Shibata M, Ito H, Itami K. Nat. Commun. 2015; 6: 6251
• 11c Ozaki K, Matsuoka W, Ito H, Itami K. Org. Lett. 2017; 19: 1930
• 11d Matsuoka W, Ito H, Itami K. Angew. Chem. Int. Ed. 2017; 56: 12224
• 11e Kitano H, Matsuoka W, Ito H, Itami K. Chem. Sci. 2018; 9: 7556
• 11f Nakamuro T, Kumazawa K, Ito H, Itami K. Synlett 2019; 30: 423
• 11g Matsuoka W, Ito H, Sarlah D, Itami K. Nat. Commun. 2021; 12: 3940
• 11h Matsuoka W, Kawahara KP, Ito H, Sarlah D, Itami K. J. Am. Chem. Soc. 2023; 145: 658
• 11i Kawahara KP, Matsuoka W, Ito H, Itami K. Angew. Chem. Int. Ed. 2020; 59: 6383
• 12 Shibata M, Ito H, Itami K. J. Am. Chem. Soc. 2018; 140: 2196

Examples of APEX reactions reported by other groups:
• 13a Schuler B, Collazos S, Gross L, Meyer G, Pérez D, Guitián E, Peña D. Angew. Chem. Int. Ed. 2014; 53: 9004
• 13b Sakakibara T, Tanaka Y, Yamaki S. Chem. Lett. 1986; 15: 797
• 13c Pham VM, Cramer N. Angew. Chem. Int. Ed. 2014; 53: 3484
• 13d Abid M, Spaeth A, Török B. Adv. Synth. Catal. 2006; 348: 2191
• 13e Dann O, Kokorudz M, Gropper R. Chem. Ber. 1954; 87: 140
• 13f Tang R.-Y, Li J.-H. Chem. Eur. J. 2010; 16: 4733
• 13g Clement JA, Sivasakthikumaran R, Mohanakrishnan AK, Sundaramoorthy S, Velmurugan D. Eur. J. Org. Chem. 2011; 569
• 13h Deb ML, Baruah B, Bhuyan PJ. Synthesis 2008; 286
• 13i Alonso M. Á, López-Alvarado P, Avendaño C, Menéndez JC. Tetrahedron 2003; 59: 2821
• 13j Laha JK, Dayal N. Org. Lett. 2015; 17: 4742
• 13k Matsuda Y, Naoe S, Oishi S, Fujii N, Ohno H. Chem. Eur. J. 2015; 21: 1463
• 13l Yamashita M, Horiguchi H, Hirano K, Satoh T, Miura M. J. Org. Chem. 2009; 74: 7481
• 13m Song G, Gong X, Li X. J. Org. Chem. 2011; 76: 7583
• 13n Lee JB, Kim GH, Jeon JH, Jeong SY, Lee S, Park J, Lee D, Kwon Y, Seo JK, Chun J.-H, Kang SJ, Choe W, Rohde J.-U, Hong SY. Nat. Commun. 2022; 13: 2421
• 13o Fort EH, Scott LT. Angew. Chem. Int. Ed. 2010; 49: 6626
• 13p Clar E, Zander M. J. Chem. Soc. 1957; 4616
• 13q Li J, Jiao C, Huang K.-W, Wu J. Chem. Eur. J. 2011; 17: 14672
• 13r Konishi A, Hirao Y, Matsumoto K, Kurata H, Kubo T. Chem. Lett. 2013; 42: 592
• 14a Ito S, Itoh T, Nakamura M. Angew. Chem. Int. Ed. 2011; 50: 454
• 14b Matsumoto A, Ilies L, Nakamura E. J. Am. Chem. Soc. 2011; 133: 6557
• 15 Musgrave OC, Webster CJ. J. Chem. Soc., Perkin Trans. 1 1974; 2260
• 16 Morrison BJ, Musgrave OC. J. Chem. Res. 2005; 2005: 549
• 17 Qarah A, Gasonoo M, Do D, Klumpp DA. Tetrahedron Lett. 2016; 57: 3711
• 18 Bashir MA, Zhang Y, Yu H, Wang B, Zhao W, Zhong F. Green Chem. 2021; 23: 5031
• 19a Tan G, You Q, Lan J, You J. Angew. Chem. Int. Ed. 2018; 57: 6309
• 19b Wang Z, Yang M, Yang Y. Org. Lett. 2018; 20: 3001
• 20a Zhang F.-G, Chen Z, Tang X, Ma J.-A. Chem. Rev. 2021; 121: 14555
• 20b Takahashi M, Ishida H, Kohmoto M. Bull. Chem. Soc. Jpn. 1976; 49: 1725
• 20c Benson SC, Palabrica CA, Snyder JK. J. Org. Chem. 1987; 52: 4610
• 21a Benson SC, Gross JL, Snyder JK. J. Org. Chem. 1990; 55: 3257
• 21b Wan Z, Snyder JK. Tetrahedron Lett. 1997; 38: 7495
• 21c Lahue BR, Wan Z.-K, Snyder JK. J. Org. Chem. 2003; 68: 4345
• 21d Benson SC, Li J.-H, Snyder JK. J. Org. Chem. 1992; 57: 5285
• 22 Hiruta K, Kitahara K, Nishi H, Tokita S. Synthesis 1982; 229
• 23 Aksenov AV, Aksenov NA, Lyakhovnenko AS, Aksenova IV. Synthesis 2009; 3439
• 24a Tokimaru Y, Ito S, Nozaki K. Angew. Chem. Int. Ed. 2018; 57: 9818
• 24b Tokimaru Y, Ito S, Nozaki K. Angew. Chem. Int. Ed. 2017; 56: 15560
• 24c Zhang X, Mackinnon MR, Bodwell GJ, Ito S. Angew. Chem. Int. Ed. 2022; 61: e202116585

For reviews, see:
• 25a Bodwell GJ, Venkataramana G, Sagar UK. In Fragments of Fullerenes and Carbon Nanotubes: Designed Synthesis, Unusual Reactions, and Coordination Chemistry. Petrukhina MA, Scott LT. Wiley; Hoboken: 2011: 367
• 25b Bodwell GJ. Chem. Rec. 2014; 14: 547
• 26 Maiti S, Achar TK, Mal P. Org. Lett. 2017; 19: 2006
• 27a Gassner C, Hesse R, Schmidt AW, Knolker H.-J. Org. Biomol. Chem. 2014; 12: 6490
• 27b Cho SH, Yoon J, Chang S. J. Am. Chem. Soc. 2011; 133: 5996
• 27c Krahl MP, Jager A, Krause T, Knolker H.-J. Org. Biomol. Chem. 2006; 4: 3215
• 28 Regar R, Mishra R, Mondal PK, Sankar J. J. Org. Chem. 2018; 83: 9547
• 29 Wang M, Kong L, Wang F, Li X. Adv. Synth. Catal. 2017; 359: 4411
• 30 Schendera E, Unkel L.-N, Quyen PP. H, Salkewitz G, Hoffmann F, Villinger A, Brasholz M. Chem. Eur. J. 2020; 26: 269
• 31 Kouznetsov VV. Tetrahedron 2009; 65: 2721
• 32 Yu Z, Zhang Y, Tang J, Zhang L, Liu Q, Li Q, Gao G, You J. ACS Catal. 2020; 10: 203
• 33 Chen C, Wang Y, Shi X, Sun W, Zhao J, Zhu Y.-P, Liu L, Zhu B. Org. Lett. 2020; 22: 4097
• 34 Klemm LH, Lawrence RF. J. Heterocycl. Chem. 1979; 16: 599
• 35a Neugebauer W, Kos AJ, Schleyer P. vR. J. Organomet. Chem. 1982; 228: 107
• 35b Ashe AJ, Kampf JW, Savla PM. J. Org. Chem. 1990; 55: 5558
• 35c Ashe AJ, Kampf JW, Savla PM. Heteroat. Chem. 1994; 5: 113
• 35d Chintala SM, Petroff JT, Barnes A, McCulla RD. J. Sulfur Chem. 2019; 40: 503
• 35e Philipp S, Dominik J, Arne B. WO 2012048781A1, 2012
• 35f Furukawa S, Suda Y, Kobayashi J, Kawashima T, Tada T, Fujii S, Kiguchi M, Saito M. J. Am. Chem. Soc. 2017; 139: 5787
• 36 Yan J, Pulis AP, Perry GJ. P, Procter DJ. Angew. Chem. Int. Ed. 2019; 58: 15675
• 37 Kawahara KP, Ito H, Itami K. Chem. Commun. 2023; 59: 1157
• 38a Ramesh E, Shankar M, Dana S, Sahoo AK. Org. Chem. Front. 2016; 3: 1126
• 38b Wang X, Gensch T, Glorius F. Org. Chem. Front. 2016; 3: 1619
• 38c Ramesh E, Guntreddi T, Sahoo AK. Eur. J. Org. Chem. 2017; 4405
• 38d Saravanan P, Anbarasan P. Org. Lett. 2014; 16: 848
• 38e Hostier T, Ferey V, Ricci G, Pardo DG, Cossy J. Org. Lett. 2015; 17: 3898
• 39 Sato R, Onodera A, Goto T, Saito M. Heterocycles 1988; 27: 2563
• 40 Kawahara KP, Ito H, Itami K. Org. Chem. Front. 2023; 10: 1880
• 41 Yang S, Cheng R, Zhang M, Bin Z, You J. ACS Catal. 2019; 9: 6188