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- Title
Cooperative Reductive Elimination: The Missing Piece in the Oxidative-Coupling Mechanistic Puzzle.
- Authors
Funes ‐ Ardoiz, Ignacio; Maseras, Feliu
- Abstract
The reaction between benzoic acid and methylphenylacetylene to form an isocoumarin is catalyzed by Cp*Rh(OAc)2 in the presence of Cu(OAc)2(H2O) as an oxidant and a leading example of oxidative-coupling reactions. Its mechanism was elucidated by DFT calculations with the B97D functional. The conventional mechanism, with separate reductive-elimination and reoxidation steps, was found to yield a naphthalene derivative as the major product by CO2 extrusion, contradicting experimental observations. The experimental result was reproduced by an alternative mechanism with a lower barrier: In this case, the copper acetate oxidant plays a key role in the reductive-elimination step, which takes place through a transition state containing both rhodium and copper centers. This cooperative reductive-elimination step would not be accessible with a generic oxidant, which, again, is in agreement with available experimental data.
- Subjects
OXIDATIVE coupling; REDUCTIVE elimination (Chemistry); DENSITY functional theory; REACTION mechanisms (Chemistry); ISOCOUMARINS
- Publication
Angewandte Chemie, 2016, Vol 128, Issue 8, p2814
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201510540