Moriarty Robert M
Department of Chemistry, University of Illinois at Chicago, Chicago, IL 60607, USA.
J Org Chem. 2005 Apr 15;70(8):2893-903. doi: 10.1021/jo050117b.
The synthetic utility of organohypervalent iodine reagents will be illustrated by their use in the alpha-hydroxydimethylacetal formation reaction from enolizable ketones, alpha-hydroxylation, alpha-tosyloxylation, alpha-alkoxylation and arylation of ketones, carbon-carbon bond formation, and intramolecular cyclopropanation using iodonium ylides. The uses of these reagents in the Hunsdiecker reaction of carboxylic acids and Hofmann rearrangement of carboxamides is presented. Specific transformation in the cubane series are discussed. The syntheses of a wide range of heterocycle structures are also presented. A unifying pathway for virtually all these diverse reactions is offered; the central features being initial attack at the iodonium center, ligand coupling, with reductive elimination of iodobenzene to yield the product.
由可烯醇化酮形成α-羟基二甲基缩醛、酮的α-羟基化、α-对甲苯磺酰氧基化、α-烷氧基化和芳基化、碳-碳键形成以及使用碘鎓叶立德进行分子内环丙烷化反应。还介绍了这些试剂在羧酸的洪斯迪克尔反应和羧酰胺的霍夫曼重排中的应用。讨论了立方烷系列中的特定转化反应。还展示了多种杂环结构的合成方法。为几乎所有这些不同反应提供了一条统一的途径；其核心特征是首先进攻碘鎓中心，进行配体偶联，然后通过还原消除碘苯生成产物。
