Highly Efficient and Facile
Aryl Transfer to Aldehydes Using ArB(OH)2-GaMe3

Xuefeng Jia; Ling Fang; Aijun Lin; Yi Pan; Chengjian Zhu

doi:10.1055/s-0028-1087552

LETTER

Highly Efficient and Facile Aryl Transfer to Aldehydes Using ArB(OH)₂-GaMe₃

Xuefeng Jia^a, Ling Fang^a, Aijun Lin^a, Yi Pan^a, Chengjian Zhu*^a,b
^a School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. of China
Fax: +86(25)83594886; e-Mail: cjzhu@nju.edu.cn;
^b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China

Abstract

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Abstract

A rapid and efficient procedure for the synthesis of diarylmethanols has successfully been achieved by the aryl transfer to aldehydes using the ArB(OH)₂-GaMe₃ combined systems in excellent yields (up to 98%) at room temperature.

Key words

aryl transfer - benzaldehyde - phenylboronic acid - trimethylgallium - diarylmethanol

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References

References and Notes

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General Experimental Procedure
The arylboronic acid (0.3 mmol, 1.5 equiv) was dissolved in anhyd toluene (2 mL) in a 20 mL flame-dried Schlenk reaction tube under argon atmosphere. A commercially available 1 M solution of Me₃Ga in toluene (0.9 mmol, 4.5 equiv) was added via syringe dropwise, and the resulting mixture was stirred for 2 h at r.t. followed by the addition of aldehyde (0.2 mmol). After completion of the reaction (monitored by TLC), the reaction solution was quenched with H₂O (3 mL) and further extracted with EtOAc (3 × 5 mL). The combined organic layer was dried over Na₂SO₄. Evaporation of the solvent gave the crude product, which was further purified by preparative TLC (PE-EtOAc, 5:1) to give corresponding pure diarylmethanols.

14

The reactivity of nitro-substituted benzaldehyde is in agreement with the experimental results in references 3c, 4d-f, but 4-nitrobenzaldehyde is not reactive in reference 2a.

15

In reference 8g,h, the mechanism of the boron-to-zinc transmetalation has been clarified by theoretical calculations and experimental study. In this process, the mixed zinc species (ArZnEt) is formed.

Supplementary Material

Supporting Information

Highly Efficient and Facile Aryl Transfer to Aldehydes Using ArB(OH)2-GaMe3

Highly Efficient and Facile Aryl Transfer to Aldehydes Using ArB(OH)₂-GaMe₃