Department of Chemistry, University of California, Berkeley, California 94720, USA.
Nat Chem. 2012 Jul 24;4(8):603-14. doi: 10.1038/nchem.1405.
Despite the tremendous advances of the past four decades, chemists are far from being able to use chiral catalysts to control the stereoselectivity of any desired reaction. New concepts for the construction and mode of operation of chiral catalysts have the potential to open up previously inaccessible reaction space. The recognition and categorization of distinct approaches seems to play a role in triggering rapid exploration of new territory. This Review both reflects on the origins as well as details a selection of the latest examples of an area that has advanced considerably within the past five years or so: the use of chiral anions in asymmetric catalysis. Defining reactions as involving chiral anions is a difficult task owing to uncertainties over the exact catalytic mechanisms. Nevertheless, we attempt to provide an overview of the breadth of reactions that could reasonably fall under this umbrella.
尽管过去四十年取得了巨大进展,但化学家们远不能使用手性催化剂来控制任何所需反应的立体选择性。构建和操作手性催化剂的新概念有可能开辟以前无法进入的反应空间。对不同方法的识别和分类似乎在触发对新领域的快速探索方面发挥了作用。这篇综述既回顾了起源,也详细介绍了过去五年左右在一个取得了相当大进展的领域的最新例子:手性阴离子在不对称催化中的应用。由于对手性催化机制的确切不确定性,将涉及手性阴离子的反应定义为是一项艰巨的任务。尽管如此,我们仍试图提供一个可以合理归入这一范畴的广泛反应的概述。