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

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

• 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.