期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 17, 期 52, 页码 14974-14986出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201101490
关键词
alkaline-earth metals; density functional calculations; hydroamination; magnesium; reaction mechanisms
The present study comprehensively explores alternative mechanistic pathways for intramolecular hydroamination of 2,2-dimethyl-4-penten-1-amine (1) by [{ToM}MgMe] (ToM=tris(4,4-dimethyl-2-oxazolinyl)phenylborate) (2) with the aid of density functional theory (DFT) calculations. A single-step amidoalkene ? cycloamine conversion through a concerted proton transfer associated with N?C ring closure has been explored as one possible mechanism; its key features have been described. This non-insertive pathway evolves via a six-centre TS structure featuring activation of the olefin unit towards nucleophilic amido attack outside the immediate vicinity of the metal centre by amino proton delivery and describes a viable mechanistic variant for alkaline-earth metal-mediated aminoalkene hydroamination. However, herein is presented sound evidence for the operation of the Mg?N amido s-bond insertive mechanism, its turnover-limiting activation barrier is found to be 5.0 kcal?mol-1 lower than for the non-insertive mechanism, for the cyclohydroamination of 2,2-disubstituted 4-aminoalkenes by a [{ToM}Mg?NHR] catalyst. The operative mechanism involves rapid equilibria of the {ToM}Mg?amidoalkene resting state 3 with its amine adduct, easily accessible and thermodynamically disfavoured, hence reversible, 1,2-olefin insertion into the Mg?N amido s-bond with ring closure at 3, linked to turnover-limiting Mg?C azacycle tether aminolysis by an adduct substrate molecule, followed by facile cycloamine liberation to regenerate the active catalyst species 3. The following aspects are in support of this scenario: 1) the derived rate law is consistent with the experimentally obtained empirical rate law; 2) the reasonable agreement between the computationally estimated and the observed value of the primary KIE; 3) the assessed effective activation barrier for turnover-limiting aminolysis matches empirically determined Eyring parameters remarkably well; and 4) the observed resistance of isolated 3 to undergo amidoalkene cycloamine/cycloamido transformation until further quantities of substrate is added is consistently explained. The herein unveiled insights into the structurereactivity relationships will undoubtedly govern the rational design of alkaline-earth metal-based catalysts and likely facilitate further advances in the area.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据