Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, United States.
J Am Chem Soc. 2012 Mar 28;134(12):5697-705. doi: 10.1021/ja3011397. Epub 2012 Mar 16.
Gold catalysis is considered one of the most important breakthroughs in organic synthesis during the past decade, but a rational understanding of ligand effects in gold catalysis is lacking. Most gold-catalyzed reactions go through three major stages: (i) electronic activation of alkyne (or allene) to generate a vinyl gold intermediate; (ii) protodeauration to generate the product and regenerate the cationic gold catalyst; (iii) decay of the active gold catalyst. Our research provides a clearer understanding of how ligands influence each of the three stages in the gold catalytic cycle. What is even more important, by not focusing on a particular gold-catalyzed reaction, we have been able to categorize most gold-catalyzed reactions and propose a ligand design protocol for each category of gold-catalyzed reactions.
金催化被认为是过去十年有机合成中最重要的突破之一，但对金催化中的配体效应缺乏合理的理解。大多数金催化反应经历三个主要阶段：（i）炔烃（或丙二烯）的电子激活，生成乙烯基金中间体；（ii）脱金生成产物并再生阳离子金催化剂；（iii）活性金催化剂的衰减。我们的研究提供了对配体如何影响金催化循环中三个阶段的更清晰的理解。更重要的是，我们没有专注于特定的金催化反应，而是能够对大多数金催化反应进行分类，并为每类金催化反应提出配体设计方案。
