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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
a   Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
,
Yuta Uetake
a   Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
b   Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
,
Hidehiro Sakurai  ∗
a   Division of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
b   Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
› Author AffiliationsThis research was supported by the JST-Mirai Program (JPMJMI18E3) and by JSPS KAKENHI grants JP19K22187 (H.S.), JP20K15279 (Y.U.), and JP22K05095 (Y.U.).
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Dedicated to Professor B. C. Ranu on the occasion of his 75th 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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2379-9191.
  • Supporting Information


Publication History

Received: 20 June 2024

Accepted after revision: 05 August 2024

Accepted Manuscript online:
05 August 2024

Article published online:
02 September 2024

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  • 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.