Asymmetric Organocatalytic Monofluorovinylations

作者：Jacobsen Christian Borch; Nielsen Martin; Worgull Dennis; Zweifel Theo; Fisker E**en; Jorgensen Karl Anker^*

来源：Journal of the American Chemical Society, 2011, 133(19): 7398-7404.

DOI：10.1021/ja110624k

The development of highly enantio- and c organocatalytic monofluorovinylations is presented. Based on the application of alpha-fluoro beta-keto-benzothiazolesulfones, the formal addition of a monofluorovinylic anion synthon to a range of acydic and cyclic enones, as well as imines, is shown. These procedures give selective access to both E- and Z-isomers of the monofluorovinylated products, which are isolated as the pure diastereoisomers in good to excellent yields with up to 99% ee. Furthermore, the application of this concept for the formation of highly enantioenriched bicylic compounds containing a monofluorovinyl moiety is also described. In addition, a mechanistic rationale for the observed E:Z-selectivities is presented.

• 出版日期2011-5-18