Red-Light-Induced N,N′-Dipropyl-1,13-dimethoxyquinacridinium-Catalyzed [3+2] Cycloaddition of Cyclopropylamines with Alkenes or Alkynes

Abstract

A red-light-mediated [3+2] annulation of cyclopropylamines with akenes or alkynes in the presence of N,N′-dipropyl-1,13-dimethoxyquinacridinium is reported. An array of cyclopentane or cyclopentene derivatives with diverse functional groups have been obtained in moderate to excellent yields under mild conditions.

Key words

photoredox catalysis - [3+2] cycloaddition - cyclopropylamines - alkenes - alkynes - dipropyldimethoxyquinacridinium

• References and Notes

• 1a Babu YS, Chand P, Bantia S, Kotian P, Dehghani A, El-Kattan Y, Lin TH, Hutchison TL, Elliott AJ, Parker CD, Ananth SL, Horn LL, Laver GW, Montgomery JA. J. Med. Chem. 2000; 43: 3482
• 1b Jia F, Hong J, Sun P.-H, Chen J.-X, Chen W.-M. Synth. Commun. 2013; 43: 2641
• 2a Trost BM, Kuo GH, Benneche T. J. Am. Chem. Soc. 1988; 110: 621
• 2b Bestmann HJ, Roth D. Synlett 1990; 751
• 2c Boyer SJ, Leahy JW. J. Org. Chem. 1997; 62: 3976
• 3a Corey EJ, Schaaf TK, Huber W, Koelliker U, Weinshenker NM. J. Am. Chem. Soc. 1970; 92: 397
• 3b Das S, Chandrasekhar S, Yadav JS, Grée R. Chem. Rev. 2007; 107: 3286
• 4a Zhou Q, Snider BB. Org. Lett. 2008; 10: 1401
• 4b Nistanaki SK, Boralsky LA, Pan RD, Nelson HM. Angew. Chem. Int. Ed. 2019; 58: 1724
• 4c Liang Y, Li Q, Wei M, Chen C, Sun W, Gu L, Zhu H, Zhang Y. Bioorg. Chem. 2020; 99: 103760
• 5a Shibata T. Adv. Synth. Catal. 2006; 348: 2328
• 5b Haberman J. Curr. Org. Chem. 2010; 14: 1139
• 6a Vaidya T, Eisenberg R, Frontier AJ. ChemCatChem 2011; 3: 1531
• 6b Fradette RJ, Kang M, West FG. Angew. Chem. Int. Ed. 2017; 56: 6335
• 7a Trost BM. Angew. Chem., Int. Ed. Engl. 1986; 25: 1
• 7b Zhang C, Lu X. J. Org. Chem. 1995; 60: 2906
• 7c Mei L.-y, Wei Y, Xu Q, Shi M. Organometallics 2012; 31: 7591
• 7d Gicquel M, Zhang Y, Aillard P, Retailleau P, Voituriez A, Marinetti A. Angew. Chem. Int. Ed. 2015; 54: 5470
• 7e Kuang Y, Ning Y, Zhu J, Wang Y. Org. Lett. 2018; 20: 2693
• 8 Kurteva VB, Afonso CA. M. Chem. Rev. 2009; 109: 6809
• 9a Boyce GR, Johnson JS. Angew. Chem. Int. Ed. 2010; 49: 8930
• 9b Boyce GR, Liu S, Johnson JS. Org. Lett. 2012; 14: 652
• 10a Ha JD, Lee J, Blackstock SC, Cha JK. J. Org. Chem. 1998; 63: 8510
• 10b Lee HB, Sung MJ, Blackstock SC, Cha JK. J. Am. Chem. Soc. 2001; 123: 11322
• 10c Maity S, Zhu M, Shinabery RS, Zheng N. Angew. Chem. Int. Ed. 2012; 51: 222
• 10d Nguyen TH, Morris SA, Zheng N. Adv. Synth. Catal. 2014; 356: 2831
• 10e Nguyen TH, Maity S, Zheng N. Beilstein J. Org. Chem. 2014; 10: 975
• 10f Muriel B, Gagnebin A, Waser J. Chem. Sci. 2019; 10: 10716
• 10g Yin Y, Li Y, Gonçalves TP, Zhan Q, Wang G, Zhao X, Qiao B, Huang K.-W, Jiang Z. J. Am. Chem. Soc. 2020; 142: 19451
• 10h White DH, Noble A, Booker-Milburn KI, Aggarwal VK. Org. Lett. 2021; 23: 3038
• 11a Prier CK, Rankic DA, MacMillan DW. C. Chem. Rev. 2013; 113: 5322
• 11b Romero NA, Nicewicz DA. Chem. Rev. 2016; 116: 10075
• 11c Skubi KL, Blum TR, Yoon TP. Chem. Rev. 2016; 116: 10035
• 11d Shang TY, Lu LH, Cao Z, Liu Y, He WM, Yu B. Chem. Commun. 2019; 55: 5408
• 11e Vega-Peñaloza A, Mateos J, Companyó X, Escudero-Casao M, Dell’Amico L. Angew. Chem. Int. Ed. 2021; 60: 1082
• 12a Ravetz BD, Pun AB, Churchill EM, Congreve DN, Rovis T, Campos LM. Nature 2019; 565: 343
• 12b Ravetz BD, Tay NE. S, Joe CL, Sezen-Edmonds M, Schmidt MA, Tan Y, Janey JM, Eastgate MD, Rovis T. ACS Cent. Sci. 2020; 6: 2053
• 13a Mei L, Veleta JM, Gianetti TL. J. Am. Chem. Soc. 2020; 142: 12056
• 13b Mei L, Gianetti T. Synlett 2021; 32: 337
• 14 Mei L, Moutet J, Stull SM, Gianetti TL. J. Org. Chem. 2021; 86: 10640
• 15a Crutchley RJ, Lever AB. P. J. Am. Chem. Soc. 1980; 102: 7128
• 15b Rillema DP, Allen G, Meyer TJ, Conrad D. Inorg. Chem. 1983; 22: 1617
• 16 Roth HG, Romero NA, Nicewicz DA. Synlett 2016; 27: 714
• 17 Red-Light-Induced ⁿPr-DMQA⁺-Catalyzed [3+2] Cycloaddition of N-Cyclopropylanilines 1 with Alkenes 2; General Procedure In a N₂ glove box, an oven-dried (overnight) Schlenk tube containing a stirring bar was charged with the appropriate substrate 1 (0.2 mmol, 1.0 equiv) and alkene 2 (1.0 mmol, 1.2 equiv). This was followed by the addition of [ⁿPr-DMQA⁺][BF₄ ^–] (1.0 mg, 0.002 mmol, 1.0 mol%) in degassed MeNO₂ (1 mL), transferred from a stock solution of the catalyst (10.0 mg) in degassed MeNO₂ (10 mL). The Schlenk tube was then sealed and removed from the glove box, and the solution was stirred at rt under red LED (λ_max = 640 nm) irradiation until the reaction was complete. The mixture was then concentrated under reduced pressure on a rotary evaporator, and the crude product was purified by flash chromatography (FC) [silica gel, hexanes–Et₂O or EtOAc (200:1 to 6:1)]. trans-N-(2-Phenylcyclopentyl)aniline (3a-I) ^10c Colorless oil; yield: 20 mg (42%). R_f = 0.3 (hexanes–EtOAc, 20:1). FC: hexanes–Et₂O (99:1). ¹H NMR (500 MHz, CDCl₃): δ = 7.31 (dd, J = 8.0, 8.0 Hz, 2 H, ArH), 7.25–7.21 (m, 3 H, ArH), 7.12 (dd, J = 8.0, 8.0 Hz, 2 H, ArH), 6.65 (dd, J = 8.0, 8.0 Hz, 1 H, ArH), 6.48 (d, J = 8.0 Hz, 2 H, ArH), 4.01 (dd, J = 12.0, 6.0 Hz, 1 H, CH), 3.46 (dd, J = 15.0, 7.5 Hz, 1 H, CH), 3.37 (bs, 1 H, NH), 2.22–2.07 (m, 3 H, CH₂), 2.02–1.94 (m, 1 H, CH₂), 1.89–1.76 (m, 2 H, CH₂). ¹³C NMR (126 MHz, CDCl₃): δ = 147.91, 140.84, 129.18, 128.77, 128.43, 126.59, 117.01, 113.32, 57.57, 48.15, 32.01, 28.94, 22.19. cis-N-(2-Phenylcyclopentyl)aniline (3a-II) ^10c Colorless oil; yield: 2 mg, 46%; R_f = 0.2 (hexanes–EtOAc, 20:1). FC: hexanes–Et₂O (99:1). ¹H NMR (500 MHz, CDCl₃): δ = 7.34–7.28 (m, 4 H, ArH), 7.22 (dd, J = 7.5, 7.5 Hz, 1 H, ArH), 7.13 (dd, J = 7.5, 7.5 Hz, 2 H, ArH), 6.67 (dd, J = 7.5, 7.5 Hz, 1 H, ArH), 6.55 (d, J = 7.5 Hz, 2 H, ArH), 3.80 (bs, 1 H, NH), 3.80 (dd, J = 13.0, 7.0 Hz, 1 H, CH), 2.93 (dd, J = 17.0, 8.0 Hz, 1 H, CH), 2.38 (ddd, J = 21.0, 14.5, 7.5 Hz, 1 H, CH₂), 2.26–2.19 (m, 1 H, CH₂), 1.94–1.82 (m, 2 H, CH₂), 1.81–1.75 (m, 1 H, CH₂), 1.66–1.58 (m, 1 H, CH₂). ¹³C NMR (126 MHz, CDCl₃): δ = 148.16, 143.83, 129.25, 128.69, 127.48, 126.54, 117.19, 113.47, 61.58, 53.27, 33.59, 33.55, 23.46.