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Synlett 2018; 29(15): 2051-2055
DOI: 10.1055/s-0037-1610259
DOI: 10.1055/s-0037-1610259
letter
Chloramine Salt Mediated Oxidative Halogenation of Terminal Alkynes with KI or NaBr: Practical Synthesis of 1-Bromoalkynes and 1-Iodoalkynes
Financial support from the National Natural Science Foundation of China (No. 21562052 and 21462055), the Guizhou Provincial Department of Science and Technology (No. LH[2014]7547, and LH[2014]7554), 15851 Talent Project Funding of Zunyi city (No. 201423), as well as National First-Rate Construction Discipline of Guizhou Province (Pharmacy) (YLXKJS-YX-04), and the Fifth Batch of Talent Base in Guizhou Province (2016) are gratefully acknowledged.
Further Information
Publication History
Received: 27 June 2018
Accepted after revision: 26 July 2018
Publication Date:
22 August 2018 (online)
Abstract
A direct oxidative halogenation of terminal alkynes has been realized using chloramine-B as the oxidant and KI or NaBr as the halogen source. This reaction enables a general and practical access to synthetically valuable 1-bromoalkynes and 1-iodoalkynes in good to excellent yields under mild reaction conditions.
Key words
oxidative halogenation - 1-bromoalkynes - 1-iodoalkynes - chloramine salt - terminal alkynesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610259.
- Supporting Information
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- 10 General Procedure for the Synthesis of 1-Iodoalkynes A 25 mL round-bottom flask with a magneton was charged with terminal alkyne 1 (0.5 mmol), KI (99 mg, 1.2 equiv), and MeCN (3 mL) under air at room temperature, and then chloramine-B (160 mg, 1.5 equiv) was added. The mixture was stirred for 2 h. After that, the reaction mixture was filtered. The filtrate was concentrated under reduced pressure. Purification of the residue by flash column chromatography on silica gel using petroleum ether/ethyl acetate as eluent afforded the desired product 2.
- 11 General Procedure for the Synthesis of 1-Bromoalkynes A 25 mL round-bottom flask with a magneton was charged with terminal alkyne 1 (0.5 mmol), NaBr (77 mg, 1.5 equiv), and MeCN/H2O (3:1, 4 mL,) under air at room temperature, and then chloramine-B (320 mg, 3.0 equiv) was added. The mixture was stirred at 70 °C for 24 h. After that, the reaction mixture was cooled to room temperature and then filtered. The filtrate was concentrated under reduced pressure. Purification of the residue by flash column chromatography on silica gel using petroleum ether/ethyl acetate as eluent afforded the desired product 3.
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