Abstract
The ligand‐controlled rhodium‐catalyzed regioselective coupling of 1,2,3‐benzotriazoles and allenes was investigated by DFT calculations. Because allylation can occur at either the N1 or N2 position of the 1,2,3‐benzotriazole, the complete Gibbs free energy profiles for both pathways were computed. A kinetic preference emerged for the experimentally observed N1 allylation with the JoSPOphos ligand, whereas N2 allylation was favored with DPEphos. Analysis of the regiodetermining oxidative addition step by using the activation strain model in conjunction with a matching energy decomposition analysis has revealed that the unprecedented N2 reaction regioselectivity is dictated by the strength of the electrostatic interactions between the 1,2,3‐benzotriazole and the rhodium catalyst. The nature of the electrostatic interaction was rationalized by analysis of the electrostatic potential maps and Hirshfeld charges: a stabilizing electrostatic interaction was found between the key atoms involved in the oxidative addition for the N2 pathway, analogous interactions are weaker in the N1 case.
Highlights
The ligand-controlled rhodium-catalyzed regioselective coupling of 1,2,3-benzotriazoles and allenes was investigated by DFT calculations
In 2014, we proposed an unprecedented rhodium (Rh) catalyzed allylation of 1,2,3-benzotriazoles
Among a series of diphosphine ligands used for the initial screening, we found that JoSPOphos (L1) gave the preference of N1 product, whereas DPEphos (L2) gave exclusive formation of the desired N2 substituted benzotriazole (Scheme 1 b)
Summary
The ligand-controlled rhodium-catalyzed regioselective coupling of 1,2,3-benzotriazoles and allenes was investigated by DFT calculations. The Gibbs free energy profile provided in Scheme 3 a reveals that the oxidative addition is the regioselectivity determining step, while the reductive elimination is the rate-determining step.
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