Dohi Toshifumi
Ritsumeikan University, Kausatsu, Shiga, Japan.
Yakugaku Zasshi. 2009 Oct;129(10):1187-99. doi: 10.1248/yakushi.129.1187.
Oxidation is synthetically important as functional group transformation as well as bond-forming method. Hypervalent iodine reagents such as phenyliodine (III) diacetate (PIDA) and phenyliodine (III) bis (trifluoroacetate) (PIFA) are one of the promising reagents for development of environmentally benign oxidations, due to their mild reactivity, low toxicity, safety, ready availability, and easy handling. Our recent challenge to this chemistry is to enhance the synthetic value of the reagents as useful alternative to highly toxic heavy metal oxidants and even rare transition metals, by pioneering a new method for enabling their efficient utilization and development of unique and new reactivities. During this course, we have succeeded in the development of new recyclable reagent 1 and its catalytic utilization, and design of a new chiral reagent 2 and its application to asymmetric oxidations. The summary of these important achievements in hypervalent iodine (III) chemistry is described herein.
氧化反应作为官能团转化以及成键方法,在合成方面具有重要意义。高价碘试剂,如二醋酸碘苯(III)(PIDA)和双(三氟乙酸)碘苯(III)(PIFA),由于其温和的反应性、低毒性、安全性、易于获得和便于操作,是开发环境友好型氧化反应的有前景的试剂之一。我们近期在这一化学领域面临的挑战是,通过开创一种能够有效利用这些试剂的新方法,并开发独特的新反应活性,来提高这些试剂作为剧毒重金属氧化剂甚至稀有过渡金属的有用替代品的合成价值。在此过程中,我们成功开发了新型可循环试剂1及其催化应用,并设计了新型手性试剂2及其在不对称氧化反应中的应用。本文将介绍高价碘(III)化学中这些重要成果的总结。