Palomo Claudio, Oiarbide Mikel, García Jesús M
Departamento de Química Orgánica I, Facultad de Química, Universidad del País Vasco, Apdo. 1072, 20080-San Sebastián, Spain.
Chem Soc Rev. 2004 Feb 20;33(2):65-75. doi: 10.1039/b202901d. Epub 2004 Jan 20.
Control of stereochemistry during aldol addition reactions has attracted considerable interest over the years as the aldol reaction is one of the most fundamental tools for the construction of new carbon-carbon bonds. Several strategies have been implemented whereby eventually any single possible stereoisomeric aldol product can be accessed by choosing the appropriate procedure. With earlier methods, stoichiometric quantities of chiral reagents were required for efficient asymmetric induction, with the auxiliary most often attached covalently to the substrate carbonyl. Lewis acid catalyzed addition reactions of silyl enolates to aldehydes (Mukaiyama reaction) later opened the way for catalytic asymmetric induction. In the last few years, both chiral metal complexes and small chiral organic molecules have been found to catalyse the direct aldol addition of unmodified ketones to aldehydes with relatively high chemical and stereochemical efficiency. These techniques along with the more recent developments in the area are discussed in this tutorial review.
多年来，羟醛加成反应中的立体化学控制一直备受关注，因为羟醛反应是构建新碳-碳键最基本的工具之一。人们已经实施了几种策略，通过选择合适的方法最终可以获得任何单一可能的立体异构羟醛产物。早期的方法需要化学计量的手性试剂来实现有效的不对称诱导，辅助基团最常共价连接到底物羰基上。后来，路易斯酸催化的烯醇硅醚与醛的加成反应（ Mukaiyama反应）为催化不对称诱导开辟了道路。在过去几年中，人们发现手性金属配合物和小型手性有机分子都能以相对较高的化学和立体化学效率催化未修饰的酮与醛的直接羟醛加成反应。本综述将讨论这些技术以及该领域的最新进展。
