Department of Chemistry, Temple University, 1901 N. 13th Street, Philadelphia, Pennsylvania 19122, United States.
School of Natural Sciences-Chemistry, University of Tasmania, Private Bag 75, Hobart, TAS 7001, Australia.
J Org Chem. 2021 May 7;86(9):6566-6576. doi: 10.1021/acs.joc.1c00375. Epub 2021 Apr 19.
Hypervalent iodine(V) reagents are a powerful class of organic oxidants. While the use of I(V) compounds Dess-Martin periodinane and IBX is widespread, this reagent class has long been plagued by issues of solubility and stability. Extensive effort has been made for derivatizing these scaffolds to modulate reactivity and physical properties but considerable room for innovation still exists. Herein, we describe the preparation, thermal stability, optimized geometries, and synthetic utility of an emerging class of I(V) reagents, Bi()-HVIs, possessing datively bound bidentate nitrogen ligands on the iodine center. Bi()-HVIs display favorable safety profiles, improved solubility, and comparable to superior oxidative reactivity relative to common I(V) reagents. The highly modular synthesis and generation of Bi()-HVIs provides a novel and convenient screening platform for I(V) reagent and reaction development.
高价碘(V)试剂是一类强大的有机氧化剂。尽管使用 I(V)化合物 Dess-Martin 过碘烷和 IBX 已经很普遍，但该试剂类长期以来一直存在溶解度和稳定性问题。人们已经进行了大量的努力来对这些支架进行衍生化，以调节反应性和物理性质，但仍然有很大的创新空间。在此，我们描述了一类新兴的高价碘(V)试剂 Bi()-HVIs 的制备、热稳定性、优化的几何形状和合成用途，该试剂具有碘中心上的配位双齿氮配体。Bi()-HVIs 表现出良好的安全性、改善的溶解度以及与常见的 I(V)试剂相比相当或更高的氧化反应性。Bi()-HVIs 的高度模块化合成和生成提供了一个新的和方便的 I(V)试剂和反应开发的筛选平台。
