Coates, GregGregCoatesTan, Hui YeeHui YeeTanKalff, CarolinCarolinKalffWhite, AndrewAndrewWhiteCrimmin, Mark RichardMark RichardCrimmin2019-07-012020-08-022019-09-02Angewandte Chemie - International Edition, 2019, 58 (36), pp.12514-125181433-7851http://hdl.handle.net/10044/1/71022A number of new magnesium and lithium silyl reagents were prepared and shown to be outstanding nucleophiles in reactions with industrially relevant fluoroolefins. These reactions result in a net transformation of either sp2 or sp3 C-F bonds into C-Si bonds by two modes of nucleophilic attack (SNV or SN2'). The methods are mild, proceeding with high chemo- and regioselectivity. Mechanistic pathways are described that lead to new substitution patterns from HFO-1234yf, HFO-1234ze and HFO-1336mzz, previously inaccessible by transition metal catalysed defluorosilylation routes.© 2019 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. This is the accepted version of the article, which has been published in final form at https://doi.org/10.1002/anie.201906825C-F Bond ActivationHFO-1234yfHFO-1234zefluorinesiliconJournal Articlehttps://www.dx.doi.org/10.1002/anie.2019068256773671521-3773