The Aryne Ene Reaction

Abstract

Intermolecular aryne ene reactions present opportunities to arylate a wide range of unsaturated substrates in a single step, whilst intramolecular reactions provide expedient access to valuable benzofused carbo- and heterocyclic frameworks. This short review will chart the development of the aryne ene reaction from initial reports that rationalise unexpected byproduct formation in competing [4+2] and [2+2] cycloadditions through to its exploitation in contemporary synthetic methodology.

1 Introduction

2 Alkene Ene Reactions

2.1 Intermolecular

2.2 Intramolecular

3 Alkyne Ene Reactions

3.1 Intermolecular

3.2 Intramolecular

4 Allene Ene Reactions

5 Aromatic Ene Reactions

6 Hetero Ene Reactions

6.1 Enols

6.2 Enamines

6.3 Imines

7 Conclusions

Key words

aryne - ene reaction - arylation - arene functionalization

Publication History

Received: 31 March 2022

Accepted after revision: 14 April 2022

Accepted Manuscript online:
14 April 2022

Article published online:
31 May 2022

• References

• 1 Alder K, Pascher F, Schmitz A. Ber. Dtsch. Chem. Ges. 1943; 76: 27

Selected general reviews on ene reactions:
• 2a Hoffman HM. R. Angew. Chem. Int. Ed. Engl. 1969; 8: 556
• 2b Snider BB. Acc. Chem. Res. 1980; 13: 426
• 2c Oppolzer W. Angew. Chem. Int. Ed. Engl. 1984; 23: 876
• 2d Baird MS. Top. Curr. Chem. 1988; 144
• 2e Mikami K, Shimizu M. Chem. Rev. 1992; 92: 1021
• 2f Dias LC. Curr. Org. Chem. 2000; 4: 305
• 2g Adam W, Krebs O. Chem. Rev. 2003; 103: 4131

Selected reviews on aryne chemistry:
• 3a Sanz R. Org. Prep. Proced. Int. 2008; 40: 215
• 3b Tadross PM, Stoltz BM. Chem. Rev. 2012; 112: 3550
• 3c Dubrovskiy AV, Markina NA, Larock RC. Org. Biomol. Chem. 2013; 11: 191
• 3d Hoffmann RW, Suzuki K. Angew. Chem. Int. Ed. 2013; 52: 2655
• 3e Pérez D, Peña D, Guitían E. Eur. J. Org. Chem. 2013; 5981
• 3f Holden C, Greaney MF. Angew. Chem. Int. Ed. 2014; 53: 5746
• 3g Yoshida S, Hosoya T. Chem. Lett. 2015; 44: 1450
• 3h García-López J.-A, Greaney MF. Chem. Soc. Rev. 2016; 45: 6766
• 3i Bhojgude SS, Bhunia A, Biju AT. Acc. Chem. Res. 2016; 49: 1658
• 3j Shi J, Li Y, Li Y. Chem. Soc. Rev. 2017; 46: 1707
• 3k Diamond OJ, Marder TJ. Org. Chem. Front. 2017; 4: 891
• 3l Idiris FI. M, Jones CR. Org. Biomol. Chem. 2017; 15: 9044
• 3m Roy T, Biju AT. Chem. Commun. 2018; 54: 2580
• 3n Shi J, Li L, Li Y. Chem. Rev. 2021; 121: 3892
• 4 Himeshima Y, Sonoda T, Kobayashi H. Chem. Lett. 1983; 12: 1211
• 5 Hoye TR, Baire B, Niu D, Willoughby PH, Woods BP. Nature 2012; 490: 208
• 6 Arnett EM. J. Org. Chem. 1960; 25: 324
• 7 Simmons HE. J. Am. Chem. Soc. 1961; 83: 1657
• 8 Wittig G, Durr H. Justus Liebigs Ann. Chem. 1964; 672: 55
• 9 Wasserman HH, Solodar AJ, Keller LS. Tetrahedron Lett. 1968; 5597
• 10 Janath TT, Jeganmohan M, Cheng M.-J, Chu A.-Y, Cheng C.-H. J. Am. Chem. Soc. 2006; 128: 2232
• 11 Candito DA, Panteleev J, Lautens M. J. Am. Chem. Soc. 2011; 133: 14200
• 12 Trinchera P, Sun W, Smith JE, Palomas D, Crespo-Otero R, Jones CR. Org. Lett. 2017; 19: 4644
• 13 Xu H, He J, Shi J, Tan L, Qiu D, Luo X, Li Y. J. Am. Chem. Soc. 2018; 140: 3555
• 14 Tabushi I, Okazaki K, Oda R. Tetrahedron 1969; 25: 4401
• 15 Friedman L, Osiewicz RJ, Rabideau PW. Tetrahedron Lett. 1968; 5735
• 16 Wasserman HH, Keller LS. Tetrahedron Lett. 1974; 15: 4355
• 17 Ahlgren G, Åkermark B. Tetrahedron Lett. 1970; 11: 3047
• 18 Garsky V, Koster DF, Arnold RT. J. Am. Chem. Soc. 1974; 96: 4207
• 19 Crews P, Beard J. J. Org. Chem. 1973; 38: 522
• 20 Chen Z, Liang J, Yin J, Yu G.-A, Liu SH. Tetrahedron Lett. 2013; 54: 5785
• 21 Dubrovskiy AV, Larock RC. Tetrahedron 2013; 69: 2789
• 22 Pérez P, Domingo LR. Eur. J. Org. Chem. 2015; 2826
• 23 Gupta S, Xie P, Xia Y, Lee D. Org. Lett. 2017; 19: 5162
• 24 Gupta S, Xie P, Xia Y, Lee D. Org. Chem. Front. 2018; 5: 2208
• 25 Minuti L, Taticchi A, Marrocchi A, Gacs-Baitz E, Galeazzi R. Eur. J. Org. Chem. 1999; 3155
• 26 Bhojgude SS, Bhunia A, Gonnade RG, Biju AT. Org. Lett. 2014; 16: 676
• 27 Suh S.-E, Chen S, Houk KN, Chenoweth DM. Chem. Sci. 2018; 9: 7688
• 28 Liu J, Li J, Ren B, Zhang Y, Xue L, Wang Y, Zhao J, Zhang P, Xu X, Li P. Adv. Synth. Catal. 2021; 363: 4734
• 29 Nakayama J, Yoshimura K. Tetrahedron Lett. 1994; 35: 2709
• 30 Watson LJ, Harrington RW, Clegg W, Hall MJ. Org. Biomol. Chem. 2012; 10: 6649
• 31 Reddy RS, Lagishetti C, Chaithanya Kiran IN, You H, He Y. Org. Lett. 2016; 18: 3818
• 32 Liu L.-L, Li Z.-J, Gu C.-Z, He L, Dai B. J. Saudi Chem. Soc. 2017; 21: 458
• 33 Sun W, Trinchera P, Kurdi N, Palomas D, Crespo-Otero R, Afshinjavid S, Javid F, Jones CR. Synthesis 2018; 50: 4591
• 34 Candito DA, Dobrovolsky D, Lautens M. J. Am. Chem. Soc. 2012; 134: 15572
• 35 Karmaker R, Mamidipalli P, Yun SY, Lee D. Org. Lett. 2013; 15: 1938
• 36 Wang H.-F, Guo L.-N, Fan Z.-B, Tang T.-H, Zi W. Org. Lett. 2021; 23: 2676
• 37 Gupta S, Lin Y, Xia Y, Wink DJ, Lee D. Chem. Sci. 2019; 10: 2212
• 38 Wasserman HH, Fernandez JM. J. Am. Chem. Soc. 1968; 90: 5322
• 39 Usieli V, Sarel S. Tetrahedron Lett. 1973; 14: 1349
• 40 Yuan W, Ma S. Org. Lett. 2014; 16: 193
• 41 Sabbasani VR, Huang G, Xia Y, Lee D. Chem. Eur. J. 2015; 21: 17210
• 42 Sabbasani VR, Huang G, Xia Y, Lee D. Org. Chem. Front. 2021; 8: 3390
• 43 Brinkley YJ, Friedman L. Tetrahedron Lett. 1972; 13: 4141
• 44 Tabushi L, Yamada H, Yoshida Z, Oda R. Bull. Chem. Soc. Jpn. 1977; 50: 285
• 45 Niu D, Hoye TR. Nat. Chem. 2014; 6: 34
• 46 Zhang J, Niu D, Brinker VA, Hoye TR. Org. Lett. 2016; 18: 5596
• 47 Truong T, Daugulis O. Chem. Sci. 2013; 4: 531
• 48 Okuma K, Matsunaga N, Nagahora N, Shioji K, Yokomori Y. Chem. Commun. 2011; 47: 5822
• 49 Pirali T, Zhang F, Miller AH, Head JL, McAusland D, Greaney MF. Angew. Chem. Int. Ed. 2012; 51: 1006
• 50 Truong T, Daugulis O. Org. Lett. 2012; 14: 5964
• 51 Aly AA, Shaker RM. Tetrahedron Lett. 2005; 46: 2679
• 52 Aly AA, Mohamed NK, Hassan AA, Mourad A.-FE. Tetrahedron 1999; 55: 1111