Asymmetric induction in thia-Diels-Alder reactions of chiral polyfluoroalkylthionocarboxylates

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• 作者：Vadim M. Timoshenko ; Sergiy A. Siry ; Alex ; er B. Rozhenko ; Yuriy G. Shermolovich
• 关键词：Thioesters ; Fluorine ; Thia-Diels-Alder reaction ; Dihydrothiopyrans ; Asymmetric induction ; DFT ; Transition state
• 刊名：Journal of Fluorine Chemistry
• 出版年：2010
• 出版时间：February 2010
• 年：2010
• 卷：131
• 期：2
• 页码：172-183
• 全文大小：920 K

文摘

A series of chiral S- or O-alkyl thionoesters have been synthesized by treatment of trifluorothioacetyl- or 2,2,3,3-tetrafluorothiopropionyl chloride with corresponding thiols or alcohols. The thia-Diels-Alder reaction of the thionoesters with symmetrical 1,3-dienes proceeds with diastereoselectivity up to 60 % . Structures of cycloaddition products and corresponding transition states have been studied at the DFT level of approximation. The experimentally observed diastereomeric excess has been referred to differences in activation energies of transition states, preceding formation of the diastereomeric cycloaducts.