Synlett 2014; 25(20): 2928-2932
DOI: 10.1055/s-0034-1379366
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Diarylmethanes through Palladium-Catalyzed Coupling of Benzylic Phosphates with Arylsilanes

Pengbo Zhang
a  Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
,
Jian Xu
a  Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
,
Yuzhen Gao
a  Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
,
Xueqin Li
a  Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
,
Guo Tang*
a  Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
,
Yufen Zhao
a  Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, P. R. of China   Fax: +86(592)2185780   Email: t12g21@xmu.edu.cn
b  Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. of China
› Author Affiliations
Further Information

Publication History

Received: 23 August 2014

Accepted after revision: 29 September 2014

Publication Date:
27 October 2014 (online)


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

 
  • 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.