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Synlett 2015; 26(01): 40-44
DOI: 10.1055/s-0034-1379162
DOI: 10.1055/s-0034-1379162
cluster
Regio- and Stereocontrolled Nucleophilic Trifluoromethylthiolation of Morita–Baylis–Hillman Carbonates
Further Information
Publication History
Received: 09 July 2014
Accepted after revision: 25 August 2014
Publication Date:
15 October 2014 (online)
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Abstract
Reactions of Morita–Baylis–Hillman carbonates with metal-free sources of trifluoromethylthio anion have been studied. The combination of CF3SiMe3/S8/KF/DMF gave the primary allylic SCF3 products through apparent SN2′ reaction whereas the use of Zard’s reagent, CF3SCO2C18H37, allowed us to intercept the fleeting secondary allylic SCF3 product.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- Supporting Information
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- 21 General Procedure for the Preparation of Compounds 3: Caution! This reaction should be conducted with a gas pressure regulator and in a well-ventilated hood to avoid exposure to toxic bis(trifluoromethyl)sulfide and higher analogues. In an oven-dried tube, sulfur (19.2 mg, 0.6 mmol) and KF (58.1 mg, 1 mmol) in anhydrous DMF (2 mL) were stirred at r.t. under dry air for 30 min. Me3SiCF3 (71 mg, 0.5 mmol) was then added to the mixture followed by addition of the MBH carbonate (0.1 mmol) and DABCO (1.12 mg, 0.01 mmol). After 22 h, the reaction went to completion (monitored by 19F NMR analysis). The reaction was quenched with H2O and extracted with Et2O. The combined organic layers were dried over MgSO4 and concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether–EtOAc, 40:1) to give the corresponding primary allylic SCF3 compound.
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For Hg(SCF3)2, see:
For AgSCF3/CuSCF3, see:
For a similar observation, see: