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Transition-Metal-Free Coupling of Alkynes with α-Bromo Carbonyl Compounds: An Efficient Approach towards β,γ-
Alkynoates and Allenoates
By Liu, Wenbo; Chen, Zhengwang; Li, Lu; Wang, Haining; Li, Chao-Jun
From Chemistry - A European Journal, 22(17), 5888-5893; 2016
Published by Wiley-VCH Verlag GmbH & Co. KGaA

Products Ethyl 2-bromoisobutyrate, CAS RN: 600-00-0

Reactants Bromoisobutyric acid, CAS RN: 2052-01-9
Ethanol, CAS RN: 64-17-5
Reagents Oxalyl chloride, CAS RN: 79-37-8
Triethylamine, CAS RN: 121-44-8
Catalysts Dimethylformamide, CAS RN: 68-12-2
Solvents Dichloromethane, CAS RN: 75-09-2
Procedure
1. Add 100 mL dry methylene chloride, α-bromo carboxylic acid (10 mmol) to a 250 mL
heat-gun dried round bottomed flask.

2. Pose the round bottomed flask with the DCM and α-bromo carboxylic acid into an ice
bath.

3. Add oxalyl chloride (11 mmol, 1.1 equivalents) and five drops DMF into the flask, the
gas formation is observed.

4. Stir the mixture for another 1 hour at room temperature.

5. Add alcohol (11 mmol), NEt3 (22 mmol, 2.2 equivalents) in 10 mL DCM dropwise into
the mixture at 0 °C.

6. Keep the mixture to stirring for another 2 hours at room temperature.

7. After 2 hours, stop the reaction.

8. Remove the volatile under vacuum.

9. Use 100 mL EtOAc and 100 mL 0.1M HCl to extract the product.

10. After the HCl wash, use another 100 mL brine to wash the organic layer.

11. Use anhydrous sodium sulfate to dry the organic layer.

12. Remove the EtOAc.

13. Purify the residue by flash column chromatography.

Transformation Esterification of Carboxylic Acids

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Scale milligram
CAS Method Number 3-356-CAS-15617446

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John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced
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