Nucleophilic Substitution of Secondary Alkyl-Substituted Propargyl Acetates: An Economic and Practical Indium Trichloride Catalyzed Access

Abstract

An economic and practical transformation from secondary alkyl-substituted propargyl acetates to a variety of nucleophilic substitution products was described. This reaction was catalyzed by inexpensive InCl₃. High yields and excellent chemoselectivity were obtained. The five-, six-, and seven-membered propargyl cyclo­ethers were also successfully constructed by this protocol.

Key words

propargyl acetate - nucleophilic substitution - indium - propargyl cycloether

References and Notes

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12

General Procedure A for the Intermolecular Substitution Reactions between Alkyl-Substituted Propargyl Acetates and Nucleophiles To a 5 mL flask were successively added propargyl acetate (0.5 mmol, 1.0 equiv), nucleophile (1.5 mmol, 3.0 equiv), MeNO₂ (2 mL) and anhyd InCl₃ (6 mg, 0.025 mmol) at r.t. Then, the mixture was magnetically stirred at appropriate temperature until the reaction was completed as monitored by TLC. The reaction mixture was cooled down to r.t., and the solvent was removed under reduced pressure. Then the residue was purified by flash chromatography on silica gel to afford the substitution product.

13

General Procedure B for the Intramolecular Substitution Reactions of Alkyl-Substituted Propargyl Acetates To a 5 mL flask were successively added propargyl acetate (1.0 mmol), MeNO₂ (2 mL) and anhyd InCl₃ (12 mg, 0.05 mmol) at r.t. Then, the mixture was magnetically stirred at 60 ˚C for 1 h. The reaction mixture was cooled down to r.t., and the solvent was removed under reduced pressure. The residue was purified by flash chromatography on silica gel to afford the intramolecular substitution product.