Functionalization of 3-Iridacyclopentenes

Margarita Gómez; Nuria Rendón; Eleuterio Álvarez; Kurt Mereiter; Manuel L Poveda; Margarita Paneque

doi:10.1002/chem.201703535

Functionalization of 3-Iridacyclopentenes

Chemistry. 2017 Nov 16;23(64):16346-16356. doi: 10.1002/chem.201703535. Epub 2017 Oct 24.

Authors

Margarita Gómez¹, Nuria Rendón¹, Eleuterio Álvarez¹, Kurt Mereiter², Manuel L Poveda¹, Margarita Paneque¹

Affiliations

¹ Instituto de Investigaciones Químicas, Departamento de Química Inorgánica, Centro de Innovación en Química Avanzada (ORFEO-CINQA), Consejo Superior de Investigaciones Científicas (CSIC), Universidad de Sevilla, Avenida Américo Vespucio 49, 41092, Sevilla, Spain.
² Department of Chemistry, Vienna University of Technology, Gestreidemarkt 9/164SC, 1060, Vienna, Austria.

PMID: 28898483
DOI: 10.1002/chem.201703535

Abstract

Members of a series of iridacyclopentenes of composition [Tp^Me2 Ir(k² -C,C-CH₂ CR'=CRCH₂ )(CO)] (Tp^Me2 =hydrotris(3,5-dimethylpyrazolyl)borate; R=R'=H, 1; R=Me, R'=H, 2; R=R'=Me, 3) have been subjected to common organic chemistry procedures for hydrogenation, cyclopropanation, epoxidation, water addition through hydroboration, cis-dihydroxylation, and ozonolysis. The stability of metallacycles 1-3, imparted by the presence of the co-ligands Tp^Me2 and CO, directs the reactivity towards the C=C double bonds, and furthermore the stereochemistry of the products formed is strongly dictated by the steric demands of the Tp^Me2 ligand. While the products obtained in some of the above-mentioned reactions are the expected ones from an organic chemistry point of view, in other cases the results differ from the outcomes of similar reactions carried out with the all-carbon counterparts.

Keywords: C=C reactivity; Wolff rearrangement; iridium; metallacycles; ring contraction.