Mechanisms, challenges, and opportunities of dual Ni/photoredox‐catalyzed C(sp2)–C(sp3) cross‐couplings. (21st September 2021)

• Record Type: Journal Article
• Authors: Yuan, Mingbin; Gutierrez, Osvaldo
• Is Part Of: Wiley interdisciplinary reviews. Volume 12:Number 3(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-09-21
• Subjects: C–C cross‐coupling -- density functional theory -- metallaphotoredox catalysis -- molecular dynamics -- olefin difunctionalization -- photoredox/nickel dual catalysis -- reaction selectivity; Chemistry, Physical and theoretical -- Periodicals; Cheminformatics -- Periodicals; Biochemistry -- Periodicals; 541.220285
• DOI: 10.1002/wcms.1573
• Languages: English
• ISSNs: 1759-0876

Abstract

Abstract: The merging of photoredox and nickel catalysis has revolutionized the field of C–C cross‐coupling. However, in comparison to the development of synthetic methods, detailed mechanistic investigations of these catalytic systems are lagging. To improve the mechanistic understanding, computational tools have emerged as powerful tools to elucidate the factors controlling reactivity and selectivity in these complex catalytic transformations. Based on the reported computational studies, it appears that the mechanistic picture of catalytic systems is not generally applicable, but is rather dependent on the specific choice of substrate, ligands, photocatalysts, etc. Given the complexity of these systems, the need for more accurate computational methods, readily available and user‐friendly dynamics simulation tools, and data‐driven approaches is clear in order to understand at the molecular level the mechanisms of these transformations. In particular, we anticipate that such improvement of theoretical methods will become crucial to advance the understanding of excited‐state properties and dynamics of key species, as well as to enable faster and unbiased exploration of reaction pathways. Further, with greater collaboration between computational, experimental, and spectroscopic communities, the mechanistic investigation of photoredox/Ni dual‐catalytic reactions is expected to thrive quickly, facilitating the design of novel catalytic systems and promoting our understanding of the reaction selectivity. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Electronic Structure Theory > Density Functional Theory Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods Abstract : Nickel/photoredox dual catalysis can forge C(sp 2 )–C(sp 3 ) bonds in both twohyphen;component and multicomponent manner. However, the operating mechanism that determines the reactivity and selectivity of key species is often less understood. Herein, current development, challenges and opportunities of the computational investigations of the mechanism are discussed.