Cook Adam, Newman Stephen G
Centre for Catalysis Research and Innovation, Department of Chemistry and Biomolecular Sciences, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
Chem Rev. 2024 May 8;124(9):6078-6144. doi: 10.1021/acs.chemrev.4c00094. Epub 2024 Apr 17.
Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods for their functionalization require them to first be converted into a more activated derivative, while recent years have seen a vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can be used toward this goal. These transformations are broadly classified into three categories. Deoxygenative functionalizations, representing derivatization of the C-O bond, enable the alcohol to act as a leaving group toward the formation of new C-C bonds. Etherifications, characterized by derivatization of the O-H bond, represent classical reactivity that has been modernized to include mild reaction conditions, diverse reaction partners, and high selectivities. Lastly, chain functionalization reactions are described, wherein the alcohol group acts as a mediator in formal C-H functionalization reactions of the alkyl backbone. Each of these three classes of transformation will be discussed in context of intermolecular arylation, alkylation, and related reactions, illustrating how catalysis can enable alcohols to be directly harnessed for organic synthesis.
醇类是有机合成中丰富且有吸引力的原料分子。它们的许多官能团化方法需要先将其转化为更具活性的衍生物，而近年来，直接利用未受保护的醇类进行构建复杂结构的转化反应数量大幅增加。本综述讨论了如何利用过渡金属催化来实现这一目标。这些转化反应大致可分为三类。脱氧官能团化反应涉及C-O键的衍生化，能使醇类作为离去基团用于形成新的C-C键。醚化反应以O-H键的衍生化为特征，代表了已实现现代化的经典反应活性，包括温和的反应条件、多样的反应伙伴和高选择性。最后，介绍了链官能团化反应，其中醇基在烷基主链的形式C-H官能团化反应中充当媒介。这三类转化反应将在分子间芳基化、烷基化及相关反应的背景下进行讨论，说明催化如何使醇类能够直接用于有机合成。
