CHAPTER 3. Catalysis by Networks of Cooperative Hydrogen Bonds

J. M. Saa, Victor J. Lillo, J. Mansilla
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引用次数: 1

Abstract

The main paradigm of today's chemistry is sustainability. In pursuing sustainability, we need to learn from chemical processes carried out by Nature and realize that Nature does not use either strong acids, or strong bases or fancy reagents to achieve outstanding chemical processes. Instead, enzyme activity leans on the cooperation of several chemical entities to avoid strong acids or bases or to achieve such an apparently simple goal as transferring a proton from an NuH unit to an E unit (NuH + E → Nu–EH). Hydrogen bond catalysis emerged strongly two decades ago in trying to imitate Nature and avoid metal catalysis. Now to mount another step in pursuing the goal of sustainability, the focus is upon cooperativity between the different players involved in catalysis. This chapter looks at the concept of cooperativity and, more specifically, (a) examines the role of cooperative hydrogen bonded arrays of the general type NuH⋯(NuH)n⋯NuH (i.e. intermolecular cooperativity) to facilitate general acid–base catalysis, not only in the solution phase but also under solvent-free and catalyst-free conditions, and, most important, (b) analyzes the capacity of designer chiral organocatalysts displaying intramolecular networks of cooperative hydrogen bonds (NCHBs) to facilitate enantioselective synthesis by bringing conformational rigidity to the catalyst in addition to simultaneously increasing the acidity of key hydrogen atoms so to achieve better complementarity in the highly polarized transition states.
第三章。协同氢键网络的催化作用
当今化学的主要范式是可持续性。在追求可持续发展的过程中,我们需要学习大自然所进行的化学过程,并认识到大自然既不使用强酸,也不使用强碱或花哨的试剂来实现卓越的化学过程。相反,酶的活性依赖于几种化学实体的合作,以避免强酸或强碱,或实现这样一个看似简单的目标,如将质子从NuH单元转移到E单元(NuH + E→Nu-EH)。氢键催化在二十年前兴起,试图模仿自然,避免金属催化。现在,为了在追求可持续性的目标上再迈出一步,重点在于参与催化的不同参与者之间的合作。本章着眼于协同性的概念,更具体地说,(a)研究一般类型NuH⋯(NuH)n⋯NuH(即分子间协同性)的协同氢键阵列的作用,以促进一般酸碱催化,不仅在溶液中,而且在无溶剂和无催化剂的条件下,而且,最重要的是,(b)分析了设计手性有机催化剂的能力,这些设计手性有机催化剂显示出分子内的合作氢键网络(NCHBs),通过给催化剂带来构象刚性,同时增加关键氢原子的酸度,从而促进对映选择性合成,从而在高度极化的过渡态中实现更好的互补。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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