Nitrile Hydration Reaction Using Copper Iodide/Cesium Carbonate/DBU in Nitromethane–Water

Jun Kuwabara; Yoshiharu Sawada; Mitsuhiro Yoshimatsu

doi:10.1055/s-0037-1609912

Synlett, Table of Contents

Synlett 2018; 29(15): 2061-2065
DOI: 10.1055/s-0037-1609912

letter

Nitrile Hydration Reaction Using Copper Iodide/Cesium Carbonate/DBU in Nitromethane–Water

Jun Kuwabara

^aDepartment of Chemistry, Faculty of Education, Gifu University, Yanagido 1-1, Gifu 501-1193, Japan Email: yoshimae@gifu-u.ac.jp

,

Yoshiharu Sawada

^bDivision of Instrumental Analysis, Life Science Research Center, Gifu University, Yanagido 1-1, Gifu 501-1193, Japan

,

Mitsuhiro Yoshimatsu*

^aDepartment of Chemistry, Faculty of Education, Gifu University, Yanagido 1-1, Gifu 501-1193, Japan Email: yoshimae@gifu-u.ac.jp

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Abstract

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Abstract

The catalytic nitrile hydration (amide formation) in a copper iodide/cesium carbonate/1,8-diazabicyclo[5.4.0]undec-7-ene/nitromethane–water system is described. The protocol is robust and reliable; it can be applied to a broad range of substrates with high chemoselectivity.

Key words

catalysis - copper iodide - nitrile hydration - nitromethane–water - primary amides

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References

References and Notes

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17 Typical Procedure for the Nitrile Hydration of Tolunitrile (1a) To a nitromethane (0.10 mL) solution of 4-methylbenzonitrile (1a, 30 mg, 0.256 mmol) were added H₂O (1.0 mL), DBU (78 mg, 0.512 mmol), copper(I) iodide (9.8 mg, 0.0512 mmol), and cesium(I) carbonate (42 mg, 0.128 mmol) at room temperature. The reaction mixture was heated at 100 °C for 1 h and then poured into water (50 mL). The organic layer was separated, and the aqueous layer was extracted with AcOEt. The combined organic layer was dried over MgSO₄. The solvent was removed under reduced pressure. The residue was purified by preparative TLC on silica gel eluting with AcOEt–n-hexane (1:1) to give 4-methylbenzamide (2a, 32 mg, 92%) as pale yellow powders. ¹H NMR (400 MHz, CDCl₃): δ = 2.40 (3 H, s, CH₃), 6.10 (2 H, br s, NH), 7.25 (2 H, d, J = 8.2 Hz, ArH), 7.71 (2 H, d, J = 8.2 Hz, ArH).

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