Dehydrosilylation of Alcohols Using Gold Nanoparticles Deposited on Citric Acid Modified Fibrillated Cellulose

Butsaratip Suwattananuruk; Yuta Uetake; Hidehiro Sakurai

doi:10.1055/a-2379-9191

Synlett, Table of Contents

Synlett 2024; 35(20): 2417-2422
DOI: 10.1055/a-2379-9191

letter

Special Issue to Celebrate the 75th Birthday of Prof. B. C. Ranu

Dehydrosilylation of Alcohols Using Gold Nanoparticles Deposited on Citric Acid Modified Fibrillated Cellulose

Butsaratip Suwattananuruk

^aDivision of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

,

Yuta Uetake

^aDivision of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

,

Hidehiro Sakurai ∗

^aDivision of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

^bInnovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

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Abstract

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Dedicated to Professor B. C. Ranu on the occasion of his 75^th birthday.

Abstract

The development of an effective catalytic system for the dehydrogenative coupling of hydrosilanes with alcohols remains an ongoing challenge, particularly for alcohol protection applications. In this study, we report the development and optimization of a highly efficient gold catalyst supported on fibrillated cellulose modified with citric acid. The catalyst exhibited remarkable catalytic activity under mild conditions with 0.01–0.05 mol% of Au loading, facilitating the formation of silyl ethers with excellent yield. Notably, our catalytic system overcomes the need for excess alcohol, typically required in such reactions, making it highly practical for alcohol protection applications. This work represents a significant advancement in the field of dehydrosilylation catalysis, offering a sustainable, efficient, and environmentally friendly approach for the synthesis of functional silanol-based materials and alcohol protection applications. The scope of substrates and the utility of the catalyst have been thoroughly studied.

Key words

gold catalysis - nanoparticles - cellulose - dehydrogenative coupling - hydrosilanes - silylation

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References

References and Notes

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14 Dehydrosilylation of Alcohols; General Procedure A reaction tube equipped with a magnetic stirrer bar was charged with Au:F-CAC (0.05 atom%), PhSiHMe₂ (2.0 mmol), the appropriate alcohol 3 (0.5 mmol), and toluene (3 mL), and the mixture was stirred for the appropriate time under an ambient atmosphere. The catalyst was then removed by filtration and washed with Et₂O (3 × 5 mL). The filtrate was concentrated under reduced pressure and the residue was purified by column chromatography (silica gel) or preparative TLC to give the silyl ether 4.
15 (Benzyloxy)(dimethyl)phenylsilane (4a) Purified by preparative TLC (hexane–EtOAc, 20:1) to give a colorless oil; yield: 82%. ¹H NMR (CDCl₃): δ = 7.62–7.60 (m, 2 H), 7.42–7.37 (m, 4 H), 7.32–7.29 (m, 3 H), 7.26–7.24 (m, 1 H), 4.70 (s, 2 H), 0.41 (s, 6 H). ¹³C NMR (CDCl₃): δ = 140.7, 137.6, 133.5, 129.7, 128.3, 127.9, 127.1, 126.5, 65.0, –1.7.
16 4-({[Dimethyl(phenyl)silyl]oxy}methyl)benzaldehyde (4f) Purified by column chromatography [silica gel, hexanes–EtOAc (9:1)] to give a colorless oil; yield: 48%. IR (diamond): 3069, 2957, 2846, 2733, 1696, 1607, 1578, 1427, 1303, 1251, 1206, 1164, 1116, 1082, 1015, 845, 826, 784, 728, 698, 648, 618, 470 cm^–1. ¹H NMR (CDCl₃): δ = 9.99 (s, 1 H), 7.86–7.81 (AA′BB′, 2 H), 7.60 (dd, J = 7.9, 1.8 Hz, 2 H), 7.49–7.43 (AA′BB′, 2 H), 7.42–7.37 (m, 3 H), 4.77 (s, 2 H), 0.44 (s, 6 H). ¹³C NMR (CDCl₃): δ = 192.1, 147.9, 137.1, 135.4, 133.5, 129.9, 129.8, 128.0, 126.6, 64.4, –1.8. HRMS (EI⁺): m/z [M^+•] calcd for C₁₆H₁₈O₂Si: 270.1076; found: 270.1082.
17 4-({[Dimethyl(phenyl)silyl]oxy}methyl)aniline (4g) Purified by gel column chromatography [silica gel, hexanes–EtOAc (3:7)] to give a brownish oil; yield: 42%. IR (diamond): 3450, 3359, 3225, 3019, 2954, 2862, 1623, 1517, 1427, 1375, 1252, 1214, 1173, 1116, 1046, 844, 823, 782, 727, 697, 642, 536, 493, 470 cm^–1. ¹H NMR (CDCl₃): δ = 7.59 (dd, J = 7.1, 2.1 Hz, 2 H), 7.43–7.34 (m, 3 H), 7.11–7.05 (AA′BB′, 2 H), 6.67–6.61 (AA′BB′, 2 H), 4.57 (s, 2 H), 3.63 (s, NH₂), 0.38 (s, 6 H). ¹³C NMR (CDCl₃): δ = 145.6, 137.8, 133.6, 130.8, 129.6, 128.4, 127.8, 115.0, 65.0, –1.6. HRMS (EI⁺) m/z [M^+•] calcd for C₁₅H₁₉NOSi: 257.1230; found: 257.1236.

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