Synlett 2014; 25(11): 1577-1584
DOI: 10.1055/s-0033-1339118
letter
© Georg Thieme Verlag Stuttgart · New York

Methanol-Promoted Borylation of Arylamines: A Simple and Green Synthetic Method to Arylboronic Acids and Arylboronates

Cong-Jun Zhao
a   Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: xuedong_welcome@snnu.edu.cn
,
Dong Xue*
a   Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: xuedong_welcome@snnu.edu.cn
,
Zhi-Hui Jia
a   Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: xuedong_welcome@snnu.edu.cn
,
Chao Wang
a   Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: xuedong_welcome@snnu.edu.cn
,
Jianliang Xiao
a   Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710062, P. R. of China   Fax: +86(29)81530727   Email: xuedong_welcome@snnu.edu.cn
b   Department of Chemistry, University of Liverpool, Liverpool L69 7ZD, UK
› Author Affiliations
Further Information

Publication History

Received: 28 February 2014

Accepted after revision: 18 April 2014

Publication Date:
28 May 2014 (online)


Abstract

A Sandmeyer borylation of arylamines via a SN2Ar pathway promoted by methanol with sodium nitrite and hydrochloric acid as diazotization agent has been developed, which provide a simple and green synthetic method to arylboronic acids and arylboronates.

Supporting Information

 
  • References and Notes


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  • 17 General Procedure for the Synthesis of Aryboronate Esters To a solution of arylamine (0.5 mmol, 1.0 equiv) in MeOH (1.0 mL) was added HCl (0.5 mL, 1.5 mmol, 3.0 equiv) followed by H2O (0.5 ml). This mixture was stirred 2 min, and the NaNO2 solution (0.25 mL) was then added. The NaNO2 solution was prepared by dissolving 35 mg of NaNO2 in H2O (0.25 mL). This mixture was stirred 30 min at 0–5 °C followed by B2pin2 (2, 381 mg, 1.5 mmol, 3.0 equiv) in MeOH (1.0 mL). This mixture was stirred 60 min. H2O (10 mL) was added to the reaction mixture, then extracted with CH2Cl2 (50 mL, 3×). The combined organic layers were washed with sat. NaHCO3, dried over Na2SO4, followed by evaporation, and the crude residue was purified by flash chromatography.
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  • 19 General Procedure for the Synthesis of Arylboronic Acids To a solution of arylamine (0.5 mmol, 1.0 equiv) in MeOH (1.0 mL) was added HCl (0.5 mL, 1.5 mmol, 3.0 equiv), followed by H2O (0.5 ml). This mixture was stirred 2 min, and the NaNO2 solution (0.25 mL) was then added. The NaNO2 solution was prepared by dissolving 35 mg of NaNO2 in H2O (0.25 mL). This mixture was stirred 30 min at 0–5 °C, followed by HCl (135 mg, 1.5 mmol, 3.0 equivalents) in MeOH (1.0 mL). This mixture was stirred 60 min. H2O (10 mL) was added to reaction mixture, then extracted with CH2Cl2 (50 mL, 3×). The combined organic layer was dried over Na2SO4, followed by evaporation to give the products.