Unexpected <i>E</i>-to-<i>Z</i> Isomerizations during the Negishi-Type Homocoupling of <i>E-</i>Iodoalkenes
The direct insertion of Zn into olefin-halide bonds is a challenge. When (<i>E</i>)-alkenyl iodides were treated with a very large excess of Zn nanoparticles, in the presence of Pd(PPh<sub>3</sub>)<sub>4</sub>, the dimerization was observed but, unexpectedly, yielding mainly <i>Z,E</i>-1,3-dienes. This apparently contrathermodynamic <i>E</i>-to-<i>Z</i> isomerization of organometallic intermediates is predicted to be general and is explained with the aid of DFT [principally M06/6-311+G(d,p)], MP2, and CCSD(T) calculations.
Authors
- Jaume Vilarrasa (ORCID: https://orcid.org/0000-0002-2522-8218)
- Anna Maria Costa (ORCID: https://orcid.org/0000-0003-4345-4750)
- Josep Samitier Martí
- Fernanda A. Crovara
Institutions
- Universitat de Barcelona (ES)
Publication Details
- Journal
- The Journal of Organic Chemistry
- Published
- 2024-09-17
- DOI
- https://doi.org/10.1021/acs.joc.3c02957
- Citations
- 1
- Primary Topic
- Fluorine in Organic Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.21
Funders
- Fundació Bosch i Gimpera