Sustainable Chemical Synthesis of 2,3-Dihydrobenzofurans/1,2,3-Trisubstituted Indanes in Water by Using a Permethylated β-Cyclodextrin-Tagged N-Heterocyclic Carbene–Gold Catalyst

Dedicated to Professor Masahiro Murakami with appreciation for his outstanding contributions as scientist and scholar.

Abstract

An environmentally friendly stereoselective synthesis of 2,3-dihydrobenzofurans and 1,2,3-trisubstituted indanes in water has been achieved by using a permethylated β-cyclodextrin-tagged N-heterocyclic carbene–gold complex. The gold catalyst can be recycled at least five times.

Key words

gold catalysis - cyclodextrins - water - catalyst recycling - benzofurans - indanes

Publikationsverlauf

Eingereicht: 30. November 2022

Angenommen nach Revision: 19. Januar 2023

Accepted Manuscript online:
23. Januar 2023

Artikel online veröffentlicht:
03. Mai 2023

• References and Notes


For reviews of benzofurans and their biological activities, see:
• 1a Shen TY, Hwang S.-B, Chang MN, Doebber TW, Lam M.-HT, Wu MS, Wang X, Han GQ, Li RZ. Proc. Natl. Acad. Sci. U. S. A. 1985; 82: 672
• 1b Ponpipom MM, Bugianesi RL, Brooker DR, Yue B.-z, Hwang S.-b, Shen T.-y. J. Med. Chem. 1987; 30: 136
• 1c Halabalaki M, Aligiannis N, Papoutsi Z, Mitakou S, Moutsatsou P, Sekeris C, Skaltsounis A.-L. J. Nat. Prod. 2000; 63: 1672
• 1d Cho JY, Baik KU, Yoo ES, Yoshikawa K, Park MH. J. Nat. Prod. 2000; 63: 1205
• 1e Pauletti PM, Araujo AR, Marx Young MC, Giesbrecht AM, da Silva Bolzani V. Phytochemistry 2000; 55: 597
• 1f Duan L, Tao H.-W, Hao X.-J, Gu Q.-Q, Zhu W.-M. Planta Med. 2009; 75: 1241
• 1g Yang X.-W, Huang X, Ma L, Wu QL, Xu W. Planta Med. 2010; 76: 1587
• 1h Zhou Z.-b, Luo J.-g, Pan K, Shan S.-m, Zhang W, Kong L.-y. Planta Med. 2013; 79: 1730
• 1i Zhang J, Chen J, Liang Z, Zhao C. Chem. Biodiv. 2014; 11: 1
• 1j Grecco SS, Lorenzi H, Tempone AG, Lago JH. G. Tetrahedron: Asymmetry 2016; 27: 793
• 2 For a review of polysubstituted indanes, see: Vilums M, Heuberger J, Heitman LH, IJzerman AP. Med. Res. Rev. 2015; 35: 1097

For reviews of the synthesis of 2,3-dihydrobenzofurans, see:
• 3a Büchi G, Chu P.-S. J. Org. Chem. 1978; 43: 3717
• 3b Büchi G, Chu P.-S. J. Am. Chem. Soc. 1981; 103: 2718
• 3c Mortlock SV, Seckington JK, Thomas EJ. J. Chem. Soc., Perkin Trans. 1 1988; 2305
• 3d Wang S, Gates BD, Swenton JS. J. Org. Chem. 1991; 56: 1979
• 3e Gates BD, Dalidowics P, Tebben A, Wang S, Swenton JS. J. Org. Chem. 1992; 57: 2135
• 3f Engler TA, Combrink KD, Letavic MA, Lynch KO. Jr, Ray JE. J. Org. Chem. 1994; 59: 6567
• 3g Engler TA, Wei D, Letavic MA, Combrink KD, Reddy JP. J. Org. Chem. 1994; 59: 6588
• 3h Asano J, Ryu Y, Chiba K, Tada M. J. Chem. Res., Synop. 1995; 124
• 3i Akai S, Morita N, Iio K, Nakamura Y, Kita Y. Org. Lett. 2000; 2: 2279
• 3j Yadav JS, Reddy BV, Kondaji G. Synthesis 2003; 1100
• 3k Itoh T, Kawai K, Hayase S, Ohara H. Tetrahedron Lett. 2003; 44: 4081
• 3l von Reuß SH, König WA. Phytochemistry 2004; 65: 3113
• 3m Hu Y, Kamitanaka T, Mishima Y, Dohi T, Kita Y. J. Org. Chem. 2013; 78: 5530
• 3n Meng L, Zhang G, Liu C, Wu K, Lei A. Angew. Chem. Int. Ed. 2013; 52: 10195
• 3o Liao L.-H, Zhang M.-M, Liao Y.-J, Yuan W.-C, Zhang X.-M. Synlett 2015; 26: 1720
• 3p Itoh T. Heterocycles 2016; 92: 1373

For reviews of the synthesis of polysubstituted indanes, see:
• 4a Borie C, Ackermann L, Nechab M. Chem. Soc. Rev. 2016; 45: 1368
• 4b Gabriele B, Mancuso R, Veltri L. Chem. Eur. J. 2016; 22: 5056

For selected examples of synthesis of polysubstituted indanes via formal [3+2] cycloadditions of benzyl alcohols with 1-phenylpropenes in organic solvents, see:
• 4c Angle SR, Arnaiz DO. J. Org. Chem. 1992; 57: 5937
• 4d Alesso E, Torviso R, Lantaño B, Erlich M, Finkielsztein LM, Moltrasio G, Aguirre JM, Brunet E. ARKIVOC 2003; (x): 283
• 4e Lantaño B, Aguirre JM, Finkielsztein L, Alesso EN, Brunet E, Moltrasio GY. Synth. Commun. 2004; 34: 625
• 4f Pizzio LR, Vázquez PG, Cáceres CV, Blanco MN, Alesso EN, Torviso MR, Lantaño B, Moltrasio GY, Aguirre JM. Appl. Catal., A 2005; 287: 1
• 4g Lantaño B, Aguirre JM, Ugliarolo EA, Benegas ML, Moltrasio GY. Tetrahedron 2008; 64: 4090
• 4h Lantaño B, Aguirre JM, Ugliarolo EA, Torviso R, Pomilio N, Moltrasio GY. Tetrahedron 2012; 68: 913
• 4i Li H.-H. Chin. Chem. Lett. 2015; 26: 320
• 4j Li Y, Zhang L, Zhang Z, Xu J, Pan Y, Xu C, Liu L, Li Z, Yu Z, Li H, Xu L. Adv. Synth. Catal. 2016; 358: 2148
• 4k Sai M. Eur. J. Org. Chem. 2019; 1102
• 4l Yang B, Dong K, Li X.-S, Wu L.-Z, Liu Q. Org. Lett. 2022; 24: 2040

For selected examples of synthesis of polysubstituted indanes, see:
• 4m Angle SR, Arnaiz DO. J. Org. Chem. 1990; 55: 3708
• 4n Watson MP, Jacobsen EN. J. Am. Chem. Soc. 2008; 130: 12594
• 4o Navarro C, Csákÿ AG. Org. Lett. 2008; 10: 217
• 4p Yuan H, Hu J, Gong Y. Tetrahedron: Asymmetry 2013; 24: 699
• 4q Zhu M, Liu J, Yu J, Chen L, Zhang C, Wang L. Org. Lett. 2014; 16: 1856
• 4r Wang Y, Wu X, Chi YR. Chem. Commun. 2017; 53: 11952
• 4s Chang M.-Y, Wu Y.-S, Tsai Y.-L, Chen H.-Y. J. Org. Chem. 2019; 84: 11699
• 4t Arredondo V, Roa DE, Gutman ES, Huynh NO, Van Vranken DL. J. Org. Chem. 2019; 84: 14745
• 4u Gao Z, Ren L, Wang R, Shi L, Wang Y, Su F, Hao H.-D. Org. Lett. 2021; 23: 5684
• 5 For our work on the dimerization in an ionic liquid, see: Morita N, Mashiko R, Hakuta D, Eguchi D, Ban S, Hashimoto Y, Okamoto I, Tamura O. Synthesis 2016; 48: 1927
• 6 For our work on formal [3+2] cycloadditions, see: Morita N, Ikeda K, Chiaki H, Araki R, Tanaka KIII, Hashimoto Y, Tamura O. Heterocycles 2021; 103: 714

Both gold(I) and gold(III) catalysts are known to have a high affinity for unsaturated bonds, but gold(III) catalysts are also known to have a high affinity for oxygen atoms; see:
• 7a Straub BF. Chem. Commun. 2004; 1726
• 7b Yamamoto Y. J. Org. Chem. 2007; 72: 7817

In general, for the same metallic Lewis acids, a higher valence has a higher charge density, thereby increasing the hardness; see:
• 7c Pearson RG. J. Am. Chem. Soc. 1963; 85: 3533

For the strategic use of oxophilic (hard) gold(III) and π-philic (soft) gold(I) catalysts, see:
• 7d Morita N, Yasuda A, Shibata M, Ban S, Hashimoto Y, Okamoto I, Tamura O. Org. Lett. 2015; 17: 2668
• 7e Morita N, Tsunokake T, Narikiyo Y, Harada M, Tachibana T, Saito Y, Ban S, Hashimoto Y, Okamoto I, Tamura O. Tetrahedron Lett. 2015; 56: 6269
• 7f Morita N, Saito Y, Muraji A, Ban S, Hashimoto Y, Okamoto I, Tamura O. Synlett 2016; 27: 1936
• 7g Morita N, Miyamoto M, Yoda A, Yamamoto M, Ban S, Hashimoto Y, Tamura O. Tetrahedron Lett. 2016; 57: 4460
• 7h Morita N, Oguro K, Takahashi S, Kawahara M, Ban S, Hashimoto Y, Tamura O. Heterocycles 2017; 95: 172
• 7i Morita N, Sano A, Sone A, Aonuma S, Matsunaga A, Hashimoto Y, Tamura O. Heterocycles 2018; 97: 719
• 8 For our work on formal [3+2] cycloadditions of benzyl alcohols with 1-phenylpropenes in an ionic liquid, see: Morita, N.; Chiaki, H.; Ikeda, K.; Tanaka, K. III.; Hashimoto, Y.; Tamura, O., Synlett 2023, in press.

For environmentally friendly syntheses of 2,3-dihydrobenzofurans, see:
• 9a Ohara H, Kiyokane H, Itoh T. Tetrahedron Lett. 2002; 43: 3041
• 9b Kouznetsov VV, Arenas DR. M, Bohórquez AR. R. Tetrahedron Lett. 2008; 49: 3097

For gold-catalyzed reactions in ionic liquids, see:
• 10a Liu X, Pan Z, Shu X, Duan X, Liang Y. Synlett 2006; 1962
• 10b Ambrogio I, Arcadi A, Cacchi S, Fabrizi G, Marinelli F. Synlett 2007; 1775
• 10c Corma A, Domínguez I, Ródenas T, Sabater MJ. J. Catal. 2008; 259: 26
• 10d Aksin Ö, Krause N. Adv. Synth. Catal. 2008; 350: 1106
• 10e Neaţu F, Pârvulescu VI, Michelet V, Gênet J.-P, Goguet A, Hardacre C. New J. Chem. 2009; 33: 102
• 10f Cui D.-M, Ke Y.-N, Zhuang D.-W, Wang Q, Zhang C. Tetrahedron Lett. 2010; 51: 980
• 10g Lempke L, Fischer T, Bell J, Kraus W, Rurack K, Krause N. Org. Biomol. Chem. 2015; 13: 3787
• 10h Lempke L, Sak H, Kubicki M, Krause N. Org. Chem. Front. 2016; 3: 1514

For reviews of sustainable synthesis and catalysis, see:
• 11a Sheldon RA. Green Chem. 2005; 7: 267
• 11b Anastas P, Eghbali N. Chem. Soc. Rev. 2010; 39: 301
• 11c Lipshutz BH, Ghorai S. Green Chem. 2014; 16: 3660
• 11d Sorella GL, Strukul G, Scarso A. Green Chem. 2015; 17: 644
• 11e Lipshutz BH, Gallou F, Handa S. ACS Sustainable Chem. Eng. 2016; 4: 5838
• 11f Marion P, Bernela B, Piccirilli A, Estrine B, Patouillard N, Guilbot J, Jérôme F. Green Chem. 2017; 19: 4973
• 11g Krause N. Curr. Opin. Green Sustainable Chem. 2017; 7: 18

For micellar gold catalysis, see:
• 12a Minkler SR. K, Lipshutz BH, Krause N. Angew. Chem. Int. Ed. 2011; 50: 7820
• 12b Minkler SR. K, Isley NA, Lippincott DJ, Krause N, Lipshutz BH. Org. Lett. 2014; 16: 724
• 12c Lempke L, Ernst A, Kahl A, Weberskirch R, Krause N. Adv. Synth. Catal. 2016; 358: 1491
• 12d Wagner B, Hiller W, Ohno H, Krause N. Org. Biomol. Chem. 2016; 14: 1579

For water-soluble-gold catalysts in water, see:
• 12e Belger K, Krause N. Org. Biomol. Chem. 2015; 13: 8556

For the synthesis and application of β-cyclodextrin-tagged NHC–gold(I) catalysts, see:
• 13a Sak H, Mawick M, Krause N. ChemCatChem 2019; 11: 5821
• 13b Zhu X, Xu G, Chamoreau L.-M, Zhang Y, Mouries-Mansuy V, Fensterbank L, Bistri-Aslanoff O, Roland S, Sollogoub M. Chem. Eur. J. 2020; 26: 15901

For reviews on cyclodextrins, see:
• 14a Szejtli J. Chem. Rev. 1998; 98: 1743
• 14b Uekama K, Hirayama F, Irie T. Chem. Rev. 1998; 98: 2045
• 14c Szejtli J. Pure Appl. Chem. 2004; 76: 1825
• 14d Prochowicz D, Kornowicz A, Lewiński J. Chem. Rev. 2017; 117: 13461
• 15 (2R*,3R*)-2-(4-Hydroxy-3-methoxyphenyl)-3-methyl-2,3-dihydrobenzofuran-5-ol (trans-3aa); Typical ProcedureAgNTf₂ (1.3 mg, 0.0034 mmol) and catalyst A (1.0 mg, 0.00058 mmol) were added to a mixture of 1,4-benzoquinone (1a; 30 mg, 0.28 mmol) and isoeugenol (2a; 46 mg, 0.28 mmol) in H₂O (1 mL), and the mixture was stirred at rt for 30 min. When the 1,4-benzoquinone (1a) was completely consumed (TLC), the product was extracted with Et₂O (2 × 2 mL). The ether layer was concentrated in vacuo and the residue was purified by column chromatography [silica gel, hexane–EtOAc (4:1)] to give a colorless oil; yield: 58 mg (81%, trans/cis = 92:8).¹H NMR (300 MHz, CDCl₃): δ = 6.96–6.80 (m, 3 H), 6.75–6.62 (m, 3 H), 5.72 (s, 1 H), 5.06 (d, J = 9.6 Hz, 1 H), 4.96 (br s, 1 H), 3.90 (s, 3 H), 3.39 (dq, J = 9.6, 6.6 Hz, 1 H), 1.38 (d, J = 6.6 Hz, 3 H). The ¹H NMR data were identical with the reported values (see ref. 3j).
• 16 A control experiment was performed to account for the presence of Brønsted acid (Tf₂NH) produced in the reaction system (for an example, see ref. 23). The reaction of p-benzoquinone (1a) with isoeugenol (2a) in the presence of Tf₂NH (1.0 mol%) at rt in H₂O for 30 min afforded product 3aa in 38% yield.
• 17 In the reaction of p-quinone 1b with isoeugenol (2a) in organic solvents (10 mol% InCl₃, CH₂Cl₂), it is known that isomer 3ba is preferentially obtained (see ref. 3j). However, in the present reaction, the sterically congested isomer 3′ba was obtained preferentially. Possibly, the latter is formed via a more-compact transition state in the cyclodextrin cavity.
• 18 (1R*,2S*,3S*)- and (1R*,2R*,3R*)-1-ethyl-5,6-dimethoxy-3-(4-methoxyphenyl)-2-methylindane (5ab and 5′ab); Typical ProcedureCatalyst A (2.6 mg, 0.0015 mmol) and AgNTf₂ (0.6 mg, 0.0015 mmol) were added to a mixture of 1-(3,4-dimethoxyphenyl)propan-1-ol (4a; 30 mg, 0.15 mmol) and trans-anethole (2a; 36 mg, 0.15 mmol) in H₂O (1 mL), and the mixture was stirred and refluxed for 1 d. When reactant 4a was completely consumed (TLC), the product was extracted with Et₂O (2 × 2 mL). The ether layer was concentrated in vacuo, and the residue was purified by column chromatography [silica gel, hexane–EtOAc (10:1)] to give an 84:16 mixture of products 5ab and 5′ab as a colorless oil; yield: 30 mg (61%).IR (KBr): 2954, 2931, 2872, 2832, 2609, 1581, 1510, 1499 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.14 (d, J = 8.7 Hz, 2 H × 16/100), 7.09 (d, J = 8.7 Hz, 2 H × 84/100)*, 6.88 (d, J = 8.7 Hz, 2 H × 84/100)*, 6.82 (s, 1 H × 84/100)*, 6.78 (s, 1 H × 16/100), 6.44 (s, 1 H × 84/100)*, 6.40 (s, 1 H × 16/100), 3.92 (s, 3 H × 84/100)*, 3.84 (s, 3 H × 16/100), 3.83 (s, 3 H × 84/100)*, 3.82 (d, J = 9.3 Hz, 1 H × 84/100)*, 3.81 (d, J = 9.0 Hz, 1 H × 16/100), 3.80 (s, 3 H × 16/100), 3.75 (s, 3 H × 84/100)*, 3.74 (s, 3 H × 16/100), 2.99–2.92 (m, 1 H × 84/100)*, 2.77–2.68 (m, 1 H × 16/100), 2.52–2.42 (m, 1 H × 84/100)*, 2.45–2.38 (m, 1 H × 16/100), 2.04–1.95 (m, 1 H × 16/100), 1.95–1.80 (m, 1 H × 16/100), 1.78–1.65 (m, 1 H × 84/100)*, 1.50–1.34 (m, 1 H × 84/100)*, 1.17 (d, J = 6.6 Hz, 1 H × 16/100), 1.05 (d, J = 6.9 Hz, 3 H × 84/100)*, 0.99 (d, J = 7.5 Hz, 3 H × 84/100)*, 0.90 (d, J = 7.5 Hz, 3 H × 16/100). ¹³C NMR (75 MHz, CDCl₃): δ = 158.2*, 148.3, 148.1*, 147.7*, 139.4*, 138.4, 138.3*, 136.6, 136.2*, 129.5*, 129.4, 113.7*, 108.2*, 108.1, 107.8*, 106.5, 58.1, 56.5*, 56.1*, 56.0*, 55.2*, 51.6, 51.1, 49.6*, 48.5*, 25.0, 22.4*, 17.6, 13.8*, 12.3*, 10.9. HRMS (EI): m/z [M⁺] calcd for C₂₁H₂₆O₃: 326.1882; found: 326.1887.
• 19 There are four possible diastereomers for 1,2,3-trisubstituted indanes 5, namely, α-(1,2-cis-2,3-trans), β-(1,2-cis-2,3-cis), γ-(1,2-trans-2,3-trans), and δ-(1,2-trans-2,3-cis), as shown in Figure 2. Stereochemical assignment of the 1,2,3-trisubstituted indanes 5 was made based on the ¹H NMR spectra, chemical shifts (ppm), coupling constants (J values), and the application of double-irradiation techniques. MacMillan et al. have reported J values for the α-(1,2-cis-2,3-trans) and γ-(1,2-trans-2,3-trans) configurations of 1,2,3-trisubstituted indanes 5 (see ref. 24); Lantaño et al. also reported similar chemical shifts (ppm) and coupling constants (J values) for the α-(1,2-cis-2,3-trans) and γ-(1,2-trans-2,3-trans) configurations of 1,2,3-trisubstituted indanes 5 (see ref. 4g).
• 20 A control experiment was performed to account for the presence of a Brønsted acid (Tf₂NH) produced in the reaction system. The reaction of benzylic alcohol 4a with trans-anethole (2b) in the presence of Tf₂NH (1.0 mol%) in refluxing water for 24 h gave no product 5ab.
• 21 Moltrasio et al. calculated the transition state of the reaction between intermediate I and trans-anethole (2a) by using the computational method AM1 (see ref. 4d). As a result, they found that the reaction proceeds preferably via the transition state shown in Scheme 7.
• 22 The enantiomeric excess of the chiral products 3 and 5 could not be determined. Based on previous work with chiral NHC–gold(I) catalyst A (ref. 13), we assume that racemic [3+2] cycloaddition products were formed. Future work will be devoted to the fine-tuning of cyclodextrin-tagged gold catalysts to synthesize enantiomerically enriched or pure cycloaddition products.
• 23 Rosenfeld DC, Shekhar S, Takemiya A, Utsunomiya M, Hartwig JF. Org. Lett. 2006; 8: 4179
• 24 MacMillan J, Martin IL, Morris DJ. Tetrahedron 1969; 25: 905