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

Publication History

Received: 30 November 2022

Accepted after revision: 19 January 2023

Accepted Manuscript online:
23 January 2023

Article published online:
03 May 2023

• References and Notes


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• 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.
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