Projects per year
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 language | English |
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Pages (from-to) | 3463–3470 |
Number of pages | 8 |
Journal | ACS Catalysis |
Volume | 13 |
Issue number | 6 |
Early online date | 23 Feb 2023 |
DOIs | |
Publication status | Published - 17 Mar 2023 |
Keywords
- Catalysis
- Cycloaddition
- Mechanism
- Parameterization
- Rhodium
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Dive into the research topics of 'Steric parameterization delivers a reciprocally predictive model for substrate reactivity and catalyst turnover in Rh-catalyzed diyne-alkyne [2+2+2] cycloadditions'. Together they form a unique fingerprint.-
EaSI-CAT - IBioIC Industry Contribution: EaSI-CAT - IBioIC Industry Contribution
Smith, A. D. (PI)
1/08/21 → 30/09/27
Project: Standard
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A biochemical boron tagging stategy: A biochemical boron tagging strategy for biomolecule visualisation and profiling
Watson, A. J. B. (PI)
1/09/22 → 31/08/24
Project: Fellowship
Datasets
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Dataset underpinning "Steric parameterization delivers a reciprocally predictive model for substrate reactivity and catalyst turnover in Rh-catalyzed diyne-alkyne [2+2+2] cycloadditions"
Watson, A. J. B. (Creator), University of St Andrews, 24 Feb 2023
DOI: 10.17630/bf157aaa-a79b-457c-976d-d273313b0e7a
Dataset
File