Department of Chemistry and FQRNT Center for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street West, Montreal, Quebec, Canada H3A 0B8.
Nat Commun. 2014 Jun 26;5:4254. doi: 10.1038/ncomms5254.
Carbon-carbon bond formation is the essence of organic synthesis. One of the most important methods for forming carbon-carbon bonds is the Barbier-Grignard-type reaction, which was discovered over a century ago. However, it is still highly desirable to further improve this process. In this article, we describe a Barbier-Grignard-type direct arylation of aldehydes by using unactivated iodides mediated by zinc and catalysed by rhodium in water. This method bypasses a number of challenges encountered by the conventional Barbier-Grignard reaction, such as strict exclusion of moisture and air, protection-deprotection of various acidic hydrogens in the substrates, and so forth. It thereby creates a safer, more convenient and more environmentally benign strategy to access the diarylmethanols and aryl alkyl alcohols, ubiquitous skeletons found in fine chemicals, biologically active molecules and pharmaceuticals. Importantly, the same reaction performed in an organic solvent proceeded sluggishly to give much inferior yields.
碳-碳键的形成是有机合成的核心。形成碳-碳键的最重要方法之一是 100 多年前发现的 Barbier-Grignard 型反应，但进一步改进这一过程仍然是非常需要的。本文描述了一种在水介质中，锌介导、铑催化、由未活化碘化物引发的醛的 Barbier-Grignard 型直接芳基化反应。该方法绕过了传统 Barbier-Grignard 反应中遇到的许多挑战，例如严格排除水分和空气、底物中各种酸性氢的保护-脱保护等。因此，它为获得二芳基甲醇和芳基烷基醇创造了一种更安全、更方便、更环保的策略，这些都是精细化学品、生物活性分子和药物中常见的骨架。重要的是，在有机溶剂中进行的相同反应进行得非常缓慢，得到的产率要低得多。
