Fischer, PaulinePaulineFischerMorris, MorganMorganMorrisMüller-Bunz, HelgeHelgeMüller-BunzEvans, PaulPaulEvans2020-11-302020-11-302020 Wiley2020-03-08European Journal of Organic Chemistry1434-193Xhttp://hdl.handle.net/10197/11758The work described details the reaction between Selectfluor® and a series of 1‐carbonyloxy and 1‐sulfonyl 2‐piperidines in order to generate 3‐fluoro‐2‐methoxypiperidines 3a–f. Their subsequent reaction with allyltrimethylsilane, in the presence of BF3 and TiCl4, is then reported. Studies involving a combination of single‐crystal X‐ray crystallography and NMR spectroscopy indicate that the allylation process is cis‐selective for both carbamate and sulfonamide variants and that optimal levels of diastereoselectivity are obtained using the N‐2‐nitrobenzene sulfonyl (2‐Ns) group. In this manner, the synthesis of a series of 2‐allyl 3‐fluoro‐substituted piperidines (5a, c–f) was achieved. The conversion of both the cis and trans‐N‐tosyl adducts (5d) into 3‐fluorinated analogues of the natural products pelletierine (10) and coniine (11) is subsequently detailed.enThis is the peer reviewed version of the following article: Fischer, P., Morris, M., Müller‐Bunz, H. and Evans, P. (2020), Synthesis and Structural Elucidation of 1,2‐Disubstituted 3‐Fluoropiperidines. Eur. J. Org. Chem., 2020: 1165-1176, which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/ejoc.202000026. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.DiastereoselectivityElectrophilic fluorinationNatural productsNeighboring group participationSynthetic methodsJournal Article202091165117610.1002/ejoc.2020000262020-03-1016/RC/3872https://creativecommons.org/licenses/by-nc-nd/3.0/ie/