Direct, catalytic hydroaminoalkylation of unactivated olefins with N-alkyl arylamines
Direct, catalytic hydroaminoalkylation of unactivated olefins with N-alkyl arylamines
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DOI：
10.1021/ja0718366
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发表时间：
2007-05-30
影响因子：
15
通讯作者：
Hartwig, John F.
中科院分区：
文献类型：
--
作者：
Herzon, Seth B.;Hartwig, John F.
报道了钽催化的N-烷基芳胺与烯烃的α-C-H键加成反应。这些反应与单-和2，2-二取代的烯烃发生，以高产率和区域选择性形成支链插入产物。该反应包括环状和非环状胺的α-C-H键的加成，以及分子内加成。NMR研究表明，起始均配型Ta（NMe 2）（5）预催化剂在溶液中转化为双-和三（N-甲基苯胺）络合物（尤其是）。氘标记的研究表明，可逆的芳烃取代基的邻位金属化的反应条件下发生。然而，几个实验表明，这种邻位金属化不在于反应途径。相反，提出这些络合物消除胺以形成N-芳基亚胺络合物，其将烯烃插入Ta-C键中并进行质子分解以再生活性催化剂并消除加成产物。
A tantalum-catalyzed addition of N-alkyl arylamine alpha-C-H bonds across olefins is reported. These reactions occur with mono- and 2,2-disubstituted olefins to form the branched insertion products in high yield and regioselectivity. The reactions encompass additions of the alpha-C-H bonds of cyclic and acyclic amines, as well as intramolecular additions. NMR studies indicate that the starting homoleptic, Ta(NMe2)(5) precatalyst converts to bis- and tris(N-methylanilide) complexes (among others) in solution. Deuterium-labeling studies suggest that reversible ortho-metalation of the arene substituent occurs under the reaction conditions. However, several experiments imply that this ortho-metalation does not lie on the reaction pathway. Instead, these complexes are proposed to eliminate amine to form N-aryl imine complexes, which insert olefins into the Ta-C bond and undergo protonolysis to regenerate the active catalyst and eliminate the addition product.