65651-78-7Relevant academic research and scientific papers
Continuous flow magnesiation of functionalized heterocycles and acrylates with TMPMgCl·LiCl
Petersen, Trine P.,Becker, Matthias R.,Knochel, Paul
supporting information, p. 7933 - 7937 (2014/08/05)
A flow procedure for the metalation of functionalized heterocycles (pyridines, pyrimidines, thiophenes, and thiazoles) and various acrylates using the strong, non-nucleophilic base TMPMgCl·LiCl is reported. The flow conditions allow the magnesiations to be performed under more convenient conditions than the comparable batch reactions, which often require cryogenic temperatures and long reaction times. Moreover, the flow reactions are directly scalable without further optimization. Metalation under flow conditions also allows magnesiations that did not produce the desired products under batch conditions, such as the magnesiation of sensitive acrylic derivatives. The magnesiated species are subsequently quenched with various electrophiles, thereby introducing a broad range of functionalities. Go with the flow: Flow conditions allow a practical metalation of functionalized heterocycles and various acrylates in the presence of the base TMPMgCl·LiCl (TMP=2,2,6,6-tetramethylpiperidyl). More convenient temperatures and very fast reaction times can usually be achieved by applying the flow conditions. Sensitive acrylic derivatives can be magnesiated under flow conditions. Furthermore, the flow reactions are readily scalable without further optimization.
Macrocyclic Lactone Formation through Sulfide Contraction. Synthesis of (+/-)-Diplodialide A
Ireland, Robert E.,Brown, Frank R.
, p. 1868 - 1880 (2007/10/02)
A methodology for the synthesis of macrocyclic β-keto-lactones from ω-hydroxy thioamides is described.The hydroxy thioamides were esterified with chloroacetyl chloride, and the resulting chloro esters underwent Eschenmoser sulfide contraction when treated with sodium iodide, diisopropylethylamine, and triethyl phosphite in acetonitrile.The β-keto lactones were obtained in 25-58 percent yield.The utility of the method was demonstrated by synthesis of diplodialide A.
