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Dédoublement cinétique d'amines par transfert d'acyle et approche synthétique du lyngbouilloside

Abstract : The development of a general and effective non-enzymatic acylative process for the kinetic resolution (KR) of amines remains, still today, a challenging field of research. In the course of this study, we were able to establish that (1S,2S)-N-acetyl-1,2-bis-trifluoromethanesulfonamidocyclohexane could be used as a highly selective acetylating agent for the kinetic resolution of primary propargylamines affording the corresponding acetamide with ees up to 96% (τc = 50%) when using an ammonium salt such as AliquatTM 336. Interestingly, a reversal of selectivity was observed in the absence of salt. We were also able to promote the kinetic resolution of primary allylamines with unprecedented levels of selectivity (ees up to 88%, τc = 45%) using a fully recyclable solid-supported ammonium salt instead of AliquatTM 336. In addition, we managed to obtain promising results in the development of a catalytic version using an achiral acyl donor in conjunction with a chiral catalyst. A synthetic approach of lyngbouilloside was also studied. Preliminary results in our group showed that the structure of the natural product may had been originally misassigned and suggested a stereochemical reassignment at C11. We managed to synthesize lyngbouilloside aglycone with the reversed stereogenic center at C11 in 19 steps and 2% overall yield.
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  • HAL Id : tel-02342593, version 1


Amandine Krieger. Dédoublement cinétique d'amines par transfert d'acyle et approche synthétique du lyngbouilloside. Chimie organique. Université Pierre et Marie Curie - Paris VI, 2014. Français. ⟨NNT : 2014PA066671⟩. ⟨tel-02342593⟩



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