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

Nobuyoshi Morita; Hitomi Chiaki; Kosaku Tanaka III; Yoshimitsu Hashimoto; Osamu Tamura; Norbert Krause

doi:10.1055/a-2016-6577

Synlett, Table of Contents

Synlett 2023; 34(12): 1425-1432
DOI: 10.1055/a-2016-6577

cluster

Special Issue Honoring Masahiro Murakami’s Contributions to Science

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

Authors

Nobuyoshi Morita∗

^aShowa Pharmaceutical University, Machida, Tokyo, 194-8543, Japan
Hitomi Chiaki

^aShowa Pharmaceutical University, Machida, Tokyo, 194-8543, Japan
Kosaku Tanaka III

^aShowa Pharmaceutical University, Machida, Tokyo, 194-8543, Japan
Yoshimitsu Hashimoto

^aShowa Pharmaceutical University, Machida, Tokyo, 194-8543, Japan
Osamu Tamura

^aShowa Pharmaceutical University, Machida, Tokyo, 194-8543, Japan
Norbert Krause∗

^bOrganic Chemistry, Dortmund University of Technology, Otto-Hahn-Strasse 6, 44227 Dortmund, Germany

Abstract

All articles of this category

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

Full Text

References

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.
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

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