The design of PINO-like hydrogen-atom-transfer catalysts

Cheng Yang; Sahil Arora; Stephen Maldonado; Derek A Pratt; Corey R J Stephenson

doi:10.1038/s41570-023-00511-z

The design of PINO-like hydrogen-atom-transfer catalysts

Nat Rev Chem. 2023 Sep;7(9):653-666. doi: 10.1038/s41570-023-00511-z. Epub 2023 Jul 18.

Authors

Cheng Yang¹, Sahil Arora¹, Stephen Maldonado^{2

3}, Derek A Pratt⁴, Corey R J Stephenson⁵

Affiliations

¹ Willard Henry Dow Laboratory, Department of Chemistry, University of Michigan, Ann Arbor, MI, USA.
² Willard Henry Dow Laboratory, Department of Chemistry, University of Michigan, Ann Arbor, MI, USA. smald@umich.edu.
³ Program in Applied Physics, University of Michigan, Ann Arbor, MI, USA. smald@umich.edu.
⁴ Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario, Canada. dpratt@uottawa.ca.
⁵ Willard Henry Dow Laboratory, Department of Chemistry, University of Michigan, Ann Arbor, MI, USA. crjsteph@umich.edu.

PMID: 37464019
DOI: 10.1038/s41570-023-00511-z

Abstract

Phthalimide-N-oxyl (PINO) is a valuable hydrogen-atom-transfer (HAT) catalyst for selective C-H functionalization. To advance and optimize PINO-catalysed HAT reactions, researchers have been focused on modifying the phthalimide core structure. Despite much effort and some notable advances, the modifications to date have centred on optimization of a single parameter of the catalyst, such as reactivity, solubility or stability. Unfortunately, the optimization with respect to one parameter is often associated with a worsening of the others. The derivation of a single catalyst structure with optimal performance across multiple parameters has therefore remained elusive. Here we present an analysis of the structure-activity relationships of PINO and its derivatives as HAT catalysts, which we hope will stimulate further development of PINO-catalysed HAT reactions and, ultimately, lead to much improved catalysts for real-world applications.

Publication types

Review