Coates Greg, Tan Hui Yee, Kalff Carolin, White Andrew J P, Crimmin Mark R
Molecular Sciences Research Hub, Imperial College London, 80 Wood Lane, Shepherds Bush, London, W12 0BZ, UK.
Angew Chem Int Ed Engl. 2019 Sep 2;58(36):12514-12518. doi: 10.1002/anie.201906825. Epub 2019 Aug 2.
A 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 sp or sp C-F bonds into C-Si bonds by two modes of nucleophilic attack (S V or S 2'). 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 catalyzed difluorosilylation routes.
制备了多种新型镁和锂硅基试剂，并证明它们在与工业相关的氟代烯烃反应中是出色的亲核试剂。这些反应通过两种亲核进攻模式（SV或S2'）将sp或sp C-F键净转化为C-Si键。该方法温和，具有高化学选择性和区域选择性。描述了从HFO-1234yf、HFO-1234ze和HFO-1336mzz产生新取代模式的机理途径，这些模式以前通过过渡金属催化的二氟硅基化路线无法实现。
