Steric parameterization delivers a reciprocally predictive model for substrate reactivity and catalyst turnover in Rh-catalyzed diyne-alkyne [2+2+2] cycloadditions

John Halford-McGuff, Alexandra M. Z. Slawin, Allan J. B. Watson*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)
2 Downloads (Pure)

Abstract

The Rh-catalyzed [2 + 2 + 2] cycloaddition of diynes and alkynes is a synthetically useful transformation that rapidly constructs complex scaffolds and has been used extensively for >70 years. Despite this utility, substrate reactivity issues persist, which are not mechanistically defined. Here, we provide a general predictive model for reactivity and turnover for this reaction. Contrary to the proposed electronic model, this is a predominately sterically driven process where productive turnover is proportional to alkyne steric parameters. This model allows for a priori prediction of catalyst loading, turnover, and reaction yield based on a simple assessment of the steric parameter (e.g., A-value) of the alkyne. The relationship is reciprocal, allowing A-values to be calculated from observed turnover.
Original languageEnglish
Pages (from-to)3463–3470
Number of pages8
JournalACS Catalysis
Volume13
Issue number6
Early online date23 Feb 2023
DOIs
Publication statusPublished - 17 Mar 2023

Keywords

  • Catalysis
  • Cycloaddition
  • Mechanism
  • Parameterization
  • Rhodium

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