10.1002/cctc.201800939
ChemCatChem
COMMUNICATION
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the reaction of air- and moisture-stable organozinc pivalates with
trialkylborates. By employment of the air- and moisture-stable
organozinc pivalates, the formation of borinic acid and borane
byproducts were completely suppressed thus providing a more
practical method for boronic ester synthesis. Furthermore, these
in situ formed boronic acid esters could be directly introduced
into Suzuki-Miyaura cross-couplings to afford biaryls in high
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General
All reactions were performed in Schlenk tubes under argon. THF was
distilled from benzophenone and sodium wire prior to use. 1H (400 or 600
MHz), 13C (101 or 151 MHz) spectra were recorded in CDCl3 solutions.
Flash chromatography was performed on silica gel (300-400 mesh).
organic pivalates were prepared according to literature.[16c]
Synthesis of boronic acids and pinacol esters 4, 6 and 7.
A dry and argon-flushed 10 mL Schlenk tube, equipped with a stirring bar
and a septum, was charged with CuI·2LiCl solution in THF (1.00 M, 0.1
mL, 0.1 mmol). The B(OiPr)3 (4.0 mmol, 2.0 equiv) was added at room
temperature. Then, a solution of the appropriate organozinc pivalate (2.0
mmol) was added dropwise over 5 min via syringe. The reaction was
stirred at room temperature overnight. Hydrochloric acid (1N, 10 mL) and
ethyl acetate (5 mL) were added and the phases were separated. The
aqueous phase was extracted with ethyl acetate (3 × 10 mL). The
combined organic layers were washed with saturated brine solution (10
mL) and dried over Na2SO4. The solvents were evaporated and the
residue was subjected to column chromatography purification on silica
yielding the respective title compound.
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General procedure of Suzuki-Miyaura cross coupling reaction
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To a solution of organozinc pivalate was charged with CuI·2LiCl solution
in THF (1.00 M, 0.2 mL, 0.2 mmol). B(OiPr)3 (4.0 mmol, 2.0 equiv) was
added at room temperature. The reaction mixture was stirred at room
temperature for 2h. ArBr (1.5 mmol) and Pd(PPh3)4 (87 mg, 0.075 mmol)
in THF (5 mL) was then added. After which, a solution of K2CO3 in water
(10%, 2.0 mL) was added and the reaction mixtures were heated to
reflux for 6 hours. Saturated aqueous NH4Cl solution (5 mL) and ethyl
acetate (5 mL) were added. The phases were separated and the
aqueous phase was extracted with ethyl acetate (3 × 10 mL). The
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mL) and dried over Na2SO4. The solvents were evaporated and the
residue was subjected to column chromatography purification on silica
yielding the biaryls.
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Acknowledgements
The authors are grateful for financial support from the National
Natural Science Foundation of China (No. 21762040, 21262030).
Keywords: boronic acid • copper catalysis •organozinc pivalate
• trialkylborate • Suzuki-Miyaura coupling
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