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

Cong-Jun Zhao; Dong Xue; Zhi-Hui Jia; Chao Wang; Jianliang Xiao

doi:10.1055/s-0033-1339118

Synlett, Inhaltsverzeichnis

Synlett 2014; 25(11): 1577-1584
DOI: 10.1055/s-0033-1339118

letter

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

Cong-Jun Zhao

^aKey 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*

^aKey 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

^aKey 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

^aKey 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

^aKey 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

^bDepartment of Chemistry, University of Liverpool, Liverpool L69 7ZD, UK

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Abstract

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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.

Key words

methanol - borylation - arylamines - arylboronic acids - arylboronates - diazotization

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Referenzen

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 NaNO₂solution 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.

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