Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
J Am Chem Soc. 2021 Feb 3;143(4):1699-1721. doi: 10.1021/jacs.0c12816. Epub 2021 Jan 19.
A growing number of organopnictogen redox catalytic methods have emerged-especially within the past 10 years-that leverage the plentiful reversible two-electron redox chemistry within Group 15. The goal of this Perspective is to provide readers the context to understand the dramatic developments in organopnictogen catalysis over the past decade with an eye toward future development. An exposition of the fundamental differences in the atomic structure and bonding of the pnictogens, and thus the molecular electronic structure of organopnictogen compounds, is presented to establish the backdrop against which organopnictogen redox reactivity-and ultimately catalysis-is framed. A deep appreciation of these underlying periodic principles informs an understanding of the differing modes of organopnictogen redox catalysis and evokes the key challenges to the field moving forward. We close by addressing forward-looking directions likely to animate this area in the years to come. What new catalytic manifolds can be developed through creative catalyst and reaction design that take advantage of the intrinsic redox reactivity of the pnictogens to drive new discoveries in catalysis?
越来越多的有机膦氧化还原催化方法已经出现——尤其是在过去 10 年中——这些方法利用了第 15 族中丰富的可逆两电子氧化还原化学。本观点的目的是为读者提供理解过去十年中有机膦催化发展的背景,着眼于未来的发展。本文阐述了磷属元素在原子结构和键合方面的基本差异,以及有机磷属元素化合物的分子电子结构,为有机膦属氧化还原反应性——最终为催化——奠定了背景。深刻理解这些基本的周期性原则,可以帮助我们理解不同的有机膦氧化还原催化模式,并为该领域的未来发展带来关键挑战。最后,我们讨论了可能在未来几年激发这一领域的前瞻性方向。通过创造性的催化剂和反应设计来开发新的催化模式,利用磷属元素的固有氧化还原反应性来推动催化领域的新发现,这将带来哪些新的催化途径?