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Formation of Substituted Oxa‐ and Azarhodacyclobutanes
Author(s) -
Dauth Alexander,
Rigling Carla,
Tsoung Jennifer,
Love Jennifer A.
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201302421
Subject(s) - selectivity , heteroatom , steric effects , chemistry , olefin fiber , alkene , yield (engineering) , ligand (biochemistry) , ethylene , medicinal chemistry , rhodium , stereochemistry , organic chemistry , catalysis , ring (chemistry) , materials science , biochemistry , receptor , metallurgy
The preparation of substituted oxa‐ and azarhodacyclobutanes is reported. After exchange of ethylene with a variety of unsymmetrically and symmetrically substituted alkenes, the corresponding rhodium–olefin complexes were oxidized with H 2 O 2 and PhINTs (Ts= p ‐toluenesulfonyl) to yield the substituted oxa‐ and azarhodacyclobutanes, respectively. Oxarhodacyclobutanes could be prepared with excellent selectivity for incorporation of the oxygen atom on the more substituted carbon atom of the alkene. At the same time, azarhodacyclobutanes showed good‐to‐excellent selectivity for heteroatom incorporation on the less substituted carbon. Furthermore, it was shown that steric modifications of the ancillary ligand have a significant influence on the selectivity of Rh–olefin complex formation as well as formation of the substituted azametallacycles.