Diiodine–Triethylsilane System: A Practical Method for Deprotection of Aryl Benzyl Ethers

Jin Jiang; Zhuo Wang

doi:10.1055/a-2414-7887

Synlett, Inhaltsverzeichnis

Synlett 2025; 36(07): 845-848
DOI: 10.1055/a-2414-7887

letter

Diiodine–Triethylsilane System: A Practical Method for Deprotection of Aryl Benzyl Ethers

Jin Jiang∗

^aSchool of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, Zigong 643000, P. R. of China

^bKey Laboratory of Green Chemistry of Sichuan Institutes of Higher Education, Zigong 643000, P. R. of China

,

Zhuo Wang

^aSchool of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, Zigong 643000, P. R. of China

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Abstract

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Abstract

A practical method for the debenzylation of aryl benzyl ethers has been developed using easy-to-operate I₂ and Et₃SiH, as well as the green solvent ethyl acetate. Halo, methoxy, ester, and nitro groups on the benzene ring of the aryl benzyl ether are compatible with this debenzylation. Control experiments revealed that Et₃SiI, generated in situ, might be the actual promoter of the procedure. This method does not require a separate desilylation reaction to obtain phenol products.

Key words

deprotection - debenzylation - iodine - triethylsilane - ethers

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References and Notes

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25 2-Naphthol (2a); Typical Procedure 2-(Benzyloxy)naphthalene (1a; 1.0 mmol, 1.0 equiv.), EtOAc (2.0 mL), Et₃SiH (1.0 mmol, 1.0 equiv), and I₂ (1.0 mmol, 1.0 equiv) were successively added to a flask at r.t., and the mixture was stirred for 30 min at r.t. EtOAc (20.0 mL) and 0.5 mol/L aq Na₂S₂O₃ (10 mL) were then added to the flask and the organic layer was washed with brine, dried (Na₂SO₄), filtered, concentrated, and purified by flash column chromatography [silica gel (100–200 mesh), PE–EtOAc (10:1)] to give a white solid; yield: 142.6 mg (99%); mp 122–123 ℃. ¹H NMR (600 MHz, CDCl₃): δ = 7.82–7.73 (m, 2 H), 7.69 (d, J = 8.4 Hz, 1 H), 7.44 (t, J = 7.8 Hz, 1 H), 7.35 (t, J = 7.8 Hz, 1 H), 7.15 (d, J = 2.4 Hz, 1 H), 7.13–7.09 (m, 1 H), 5.12 (s, 1 H). ¹³C NMR (150 MHz, CDCl₃): δ = 153.4, 136.1, 130.0, 129.1, 127.9, 126.7, 126.5, 123.8, 117.9, 109.7.