Institut Lavoisier-Versailles, UMR 8180, Université de Versailles St-Quentin-en-Yvelines, 45 avenue des Etats-Unis, 78035, Versailles, France.
Chemistry. 2011 Nov 11;17(46):12852-71. doi: 10.1002/chem.201101755. Epub 2011 Oct 19.
This review article presents how nitrogen-centred Lewis bases were modified in order to increase their reactivity in catalytic processes. As examples, we focus on alcohol acylation and Morita-Baylis-Hilman reactions in order to showcase the fundamental parameters at play in transformations initiated by catalysts bearing respectively an active sp(2) or sp(3) nitrogen atoms. These two aspects are epitomised by two leading compounds, the Steglich base 4-dimethylaminopyridine (DMAP), and 1,4-diazabicyclo[2.2.2]octane (DABCO). Throughout this review, we stress the role played and the information brought by physical organic chemistry. Comprehension of these complex transformations relies on the fundamental knowledge of parameters, such as, nucleophilicity, nucleofugality, Lewis basicity, and crucially also the knowledge of their divergent impacts on each elementary step of the catalytic cycle.
这篇综述文章介绍了如何修饰以氮为中心的路易斯碱，以提高它们在催化过程中的反应性。作为例子，我们专注于醇酰化和 Morita-Baylis-Hilman 反应，以展示由分别含有活性 sp(2)或 sp(3)氮原子的催化剂引发的转化中的基本参数。这两个方面由两个领先的化合物来代表，即 Steglich 碱 4-二甲氨基吡啶（DMAP）和 1,4-二氮杂二环[2.2.2]辛烷（DABCO）。在整篇综述中，我们强调了物理有机化学所扮演的角色和带来的信息。对这些复杂转化的理解依赖于对参数的基本认识，例如亲核性、离去性、路易斯碱性，以及至关重要的是对它们在催化循环的每个基本步骤中不同影响的认识。
