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Synlett 2014; 25(20): 2928-2932
DOI: 10.1055/s-0034-1379366
DOI: 10.1055/s-0034-1379366
letter
Synthesis of Diarylmethanes through Palladium-Catalyzed Coupling of Benzylic Phosphates with Arylsilanes
Further Information
Publication History
Received: 23 August 2014
Accepted after revision: 29 September 2014
Publication Date:
27 October 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201420/lookinside/thumbnails/10.1055-s-0034-1379366-1.jpg)
Abstract
An efficient approach to the benzylation of arenes has been developed. The reactions described provide straightforward access to diarylmethanes through Pd-catalyzed coupling of benzylic phosphates with arylsilanes in good to excellent yields. The reaction tolerates a wide range of functionalities such as halide, alkoxyl, and nitro groups.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- Supporting Information
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References and notes
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- 23 Preparation of Benzylic Phosphates; General Procedure: To a flask charged with the requisite benzyl alcohol (20.0 mmol), Et3N (4.2 mL, 30.0 mmol, 150 mol%), DMAP (244 mg, 2.0 mmol, 10 mol%), and THF (5 mL), was added neat diethyl chlorophosphate (2.9 mL, 20.0 mmol, 100 mol%) over a 30 min period at r.t. The resultant white, heterogeneous mixture was stirred for 16 h then poured into a solution of 1 M KHSO4 (50 mL). The separated organic phase was then washed with sat. aq NaHCO3 (30 mL) and brine (30 mL), before it was dried over MgSO4, filtered, and concentrated to give a crude oil. The crude oil was purified by flash chromatography (petroleum ether–EtOAc, 5:1, v/v) to give the product 1a.
- 24 Hiyama Cross-Coupling; General Procedure: An oven-dried Schlenk tube with Pd(OAc)2 (5 mol%) and dppp (10 mol%) was evacuated and purged with argon three times. A mixture of TBAF (1 M in THF, 0.36 mL), 2a (0.45 mmol), and benzylic phosphate (1a; 0.30 mmol) was dissolved in freshly distilled 1,4-dioxane (1.0 mL), and added at r.t. The reaction mixture was heated with stirring at 100 °C for 24 h, then cooled to ambient temperature and transferred to a round-bottom flask. Silica gel (2.0 g) was added and the solvent was removed under reduced pressure to afford a free-flowing powder. The powder was then dry-loaded onto a silica gel column and purified by flash chromatography using petroleum as the eluent to give the desired product 3aa. All products were synthesized according to this procedure. Yield: 45 mg (90%); colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.30–7.24 (m, 4 H), 7.20–7.14 (m, 6 H), 3.96 (s, 2 H). 13C NMR (100 MHz, CDCl3): δ = 141.5, 129.1, 128.7, 126.3, 42.3.
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