Warsitz Michael, Doye Sven
Institut für Chemie, Universität Oldenburg, Carl-von-Ossietzky-Strasse 9-11, 26129, Oldenburg, Germany.
Chemistry. 2020 Nov 26;26(66):15121-15125. doi: 10.1002/chem.202003223. Epub 2020 Oct 22.
The regioselective conversion of alkyl-substituted alkenes into linear hydroaminoalkylation products represents a strongly desirable synthetic transformation. In particular, such conversions of N-methylamine derivatives are of great scientific interest, because they would give direct access to important amines with unbranched alkyl chains. Herein, we present a new one-pot procedure that includes an initial alkene hydroaminoalkylation with an α-silylated amine substrate and a subsequent protodesilylation reaction that delivers linear hydroaminoalkylation products with high selectivity from simple alkyl-substituted alkenes. For that purpose, new titanium catalysts have been developed, which are able to activate the α-C-H bond of more challenging α-silylated amine substrates. In addition, a direct relationship between the ligand structure of the new catalysts and the obtained regioselectivity is described.
将烷基取代的烯烃区域选择性转化为线性氢胺烷基化产物是一种非常理想的合成转化反应。特别是，N-甲胺衍生物的这种转化具有重大的科学意义，因为它们可以直接合成具有直链烷基的重要胺类。在此，我们提出了一种新的一锅法，该方法包括首先用α-硅烷基化胺底物对烯烃进行氢胺烷基化，随后进行原硅烷基化反应，从而从简单的烷基取代烯烃中以高选择性得到线性氢胺烷基化产物。为此，已开发出新型钛催化剂，其能够活化更具挑战性的α-硅烷基化胺底物的α-C-H键。此外，还描述了新型催化剂的配体结构与所得区域选择性之间的直接关系。
