Bay-Region-Selective Annulative π-Extension (APEX) of Perylene Diimides with Arynes

Published as part of the 30 Years SYNLETT – Pearl Anniversary Issue

Abstract

A bay-region-selective annulative π-extension (APEX) reaction of perylene diimides (PDIs) has been achieved by means of in-situ generated reactive aryne intermediates. This method provides an efficient one-pot π-extension at the short axis of PDIs in a sequential manner. Mechanistically, an inverse-electron-demand Diels–Alder reaction might be operative for the transformation.

Key words

annulative π-extension - perylene diimides - arynes - Diels–Alder reaction - coronene diimides - polycyclic aromatic hydrocarbons

• References and Notes

• 1 Current address: Graduate School of Science, The University of Tokyo, Hongo, Tokyo 113-0033, Japan.
• 2 For a review on perylene diimides, see: Chen L, Li C, Müllen K. J. Mater. Chem. C 2014; 2: 1938
• 3a Soh N, Ueda T. Talanta 2011; 85: 1233
• 3b Ramírez MG, Morales-Vidal M, Navarro-Fuster V, Boj PG, Quintana JA, Villalvilla JM, Retolaza A, Merino S, Díaz-García MA. J. Mater. Chem. C 2013; 1: 1182
• 3c Würthner F, Saha-Möller CR, Fimmel B, Ogi S, Leowanawat P, Schmidt D. Chem. Rev. 2016; 116: 962
• 3d Kojima M, Tamoto A, Aratani N, Yamada H. Chem. Commun. 2017; 53: 5698
• 3e Nagarajan K, Mallia AR, Muraleedharan K, Hariharan M. Chem. Sci. 2017; 8: 1776
• 4a Battagliarin G, Li C, Enkelmann V, Müllen K. Org. Lett. 2011; 13: 3012
• 4b Sun J, Zhong F, Zhao J. Dalton Trans. 2013; 42: 9595
• 4c Ito S, Hiroto S, Shinokubo H. Chem. Lett. 2014; 43: 1309
• 5a Pschirer NG, Kohl C, Nolde F, Qu J, Müllen K. Angew. Chem. Int. Ed. 2006; 45: 1401
• 5b Zhao X, Xiong Y, Ma J, Yuan Z. J. Phys. Chem. A 2016; 120: 7554
• 6a Avlasevich Y, Müller S, Erk P, Müllen K. Chem. Eur. J. 2007; 13: 6555
• 6b Li Y, Xu L, Liu T, Yu Y, Liu H, Li Y, Zhu D. Org. Lett. 2011; 13: 5692
• 6c Chaolumen Enno H, Murata M, Wakamiya A, Murata Y. Chem. Asian. J. 2014; 9: 3136
• 6d Calbo J, Doncel-Giménez A, Aragó J, Ortí E. Theor. Chem. Acc. 2018; 137: 27

For reviews on APEX reaction of aromatics, see:
• 7a Ito H, Ozaki K, Itami K. Angew. Chem. Int. Ed. 2017; 56: 11144
• 7b Ito H, Segawa Y, Murakami K, Itami K. J. Am. Chem. Soc. 2019; 141: 3

For our contributions towards APEX reactions of nonfunctionalized PAHs, see:
• 8a Ozaki K, Kawasumi K, Shibata M, Ito H, Itami K. Nat. Commun. 2015; 6: 6251
• 8b Yano Y, Ito H, Segawa Y, Itami K. Synlett 2016; 27: 2081
• 8c Kato K, Segawa Y, Itami K. Can. J. Chem. 2017; 95: 329
• 8d Ozaki K, Zhang H, Ito H, Lei A, Itami K. Chem. Sci. 2013; 4: 3416
• 8e Ozaki K, Murai K, Matsuoka W, Kawasumi K, Ito H, Itami K. Angew. Chem. Int. Ed. 2017; 56: 1361
• 8f Matsuoka W, Ito H, Itami K. Angew. Chem. Int. Ed. 2017; 56: 12224

For a definition of the APEX reaction, see:
• 8g Segawa Y, Ito H, Itami K. Nat. Rev. Mater. 2016; 1: 15002

For selected APEX reactions of nonfunctionalized heteroaromatics, see:
• 9a Paria S, Reiser O. Adv. Synth. Catal. 2014; 356: 557
• 9b Ozaki K, Matsuoka W, Ito H, Itami K. Org. Lett. 2017; 19: 1930
• 9c Kitano H, Matsuoka W, Ito H, Itami K. Chem. Sci. 2018; 9: 7556

For selected bay-region selective APEX reactions, see:
• 10a Clar E. Ber. Dtsch. Chem. Ges. 1932; 65: 846
• 10b Clar E, Zander M. J. Chem. Soc. 1957; 4616
• 10c Fort EH, Donovan PM, Scott LT. J. Am. Chem. Soc. 2009; 131: 16006
• 10d Fort EH, Scott LT. J. Mater. Chem. 2011; 21: 1373
• 10e Fort EH, Jeffreys MS, Scott LT. Chem. Commun. 2012; 48: 8102
• 10f Fort EH, Scott LT. Angew. Chem. Int. Ed. 2010; 49: 6626
• 10g Li J, Jiao C, Huang K.-W, Wu J. Chem. Eur. J. 2011; 17: 14672

For the utilization of arynes, see:
• 10h Stork G, Leonia NJ, Matsuda K. US 3364274, 1968
• 10i Stork G, Leonia NJ, Matsuda K. US 3364275, 1968
• 10j Fort EH, Scott LT. Tetrahedron Lett. 2011; 52: 2051
• 10k Konishi A, Hirao Y, Matsumoto K, Kurata H, Kubo T. Chem. Lett. 2013; 42: 592
• 10l Schuler B, Collazos S, Gross L, Meyer G, Pérez D, Guitián E, Peña D. Angew. Chem. Int. Ed. 2014; 53: 9004
• 10m Xu F, Xiao X, Hoye TR. Org. Lett. 2016; 18: 5636

For reviews on benzyne chemistry, see:
• 11a Takikawa H, Nishii A, Sakai T, Suzuki K. Chem. Soc. Rev. 2018; 47: 8030
• 11b Roy T, Biju TT. Chem. Commun. 2018; 54: 2580
• 11c Shi J, Li Y, Li Y. Chem. Soc. Rev. 2017; 46: 1707
• 11d Bhojgude SS, Bhunia A, Biju AT. Acc. Chem. Res. 2016; 49: 1658
• 11e Pérez D, Peña D, Guitián E. Eur. J. Org. Chem. 2013; 5981
• 12 Cioslowski J, Piskorz P, Moncrieff D. J. Am. Chem. Soc. 1998; 120: 1695 ; and references cited therein
• 13a Saito N, Nakamura K, Shibano S, Ide S, Minami M, Sato Y. Org. Lett. 2013; 15: 386
• 13b For a review on heterocyclic arynes, see: Goetz AE, Shah TK, Garg NK. Chem. Commun. 2015; 51: 34
• 14a Sanyal S, Manna AK, Pati SK. J. Phys. Chem. C 2013; 117: 825
• 14b Zhang C, Shi K, Jiajun X, Lei T, Yan Q, Wang J.-Y, Pei J, Zhao D. Chem. Commun. 2015; 51: 7144
• 14c Yang M, Zhou H, Li Y, Zhang Q, Li J, Zhang C, Zhou C, Yu C. J. Mater. Chem. B 2017; 5: 6572
• 14d Paul SC, Cammarata V. J. Electrochem. Soc. 2018; 165: G116
• 15 For a review on recent inverse-electron-demand Diels–Alder reactions, see: Jiang X, Wang R. Chem. Rev. 2013; 113: 5515
• 16 We also calculated each stationary point and transition state by other basis sets (See SI for details).
• 17 3a; Typical Procedure A screw-capped glass tube containing a magnetic stirrer bar was charged sequentially with the dimesityl PDI 1a (100 μmol, 1.0 equiv, 62.4 mg), KF (0.51 mmol, 5.0 equiv, 29.5 mg), PhCN (2.0 mL), and 2-(trimethylsilyl)phenyl triflate (2a, 0.20 mmol, 2.0 equiv, 60.0 mg) under a stream of N₂. The mixture was stirred at 160 °C for 48 h, cooled to r.t., and passed through a short pad of silica gel (eluent: CHCl₃). The organic solvent was removed under reduced pressure to give a crude mixture that was analyzed by ¹H NMR (CDCl₃) with CH₂Br₂ as an internal standard. The residue was the purified by flash column chromatography (silica gel) to afford a mixture of 3aa and 4aa, which was further purified by gel-permeation chromatography to give 3aa as a red solid; yield: 26.4 mg (37.7 μmol, 37% isolated). ¹H NMR (400 MHz, CDCl₃): δ = 10.2 (s, 2 H), 9.32–9.27 (m, 2 H), 9.24 (d, J = 8.4 Hz, 2 H), 9.10 (d, J = 8.4 Hz, 2 H), 8.19–8.13 (m, 2 H), 7.13 (s, 4 H), 2.42 (s, 6 H), 2.25 (s, 12 H). ¹³C NMR (150 MHz, CDCl₃): δ = 163.5, 163.3, 138.8, 135.2, 134.2, 131.1, 130.0, 129.51, 129.47, 129.3, 129.2, 129.0, 128.6, 127.9, 125.1, 124.2, 123.3, 122.9, 122.5, 21.3, 17.9. HRMS (MALDI-TOF): m/z [M + H]⁺ calcd for C₄₈H₃₃N₂O₄: 701.2435; found: 701.2434.