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Asymmetric Ring Opening of Benzo‐7‐oxabicyclo[2.2.1]heptadienes with Cationic Rhodium Complexes
Author(s) -
Preetz Angelika,
Kohrt Christina,
Drexler HansJoachim,
Torrens Antoni,
Buschmann Helmut,
Lopez Monica Garcia,
Heller Detlef
Publication year - 2010
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201000236
Subject(s) - chemistry , rhodium , cationic polymerization , ring (chemistry) , nucleophile , stereochemistry , nuclear magnetic resonance spectroscopy , medicinal chemistry , catalysis , organic chemistry
The efficient design of stereochemically challenging ring systems by ring opening of heterobicyclic alkenes has become a very important reaction in the chemistry of CC and CX bond formation. By using the hitherto applied in situ technique for the generation of the μ 2 ‐bridged, dimeric neutral rhodium complexes, however, the catalytically active species and its concentration remained unidentified. Furthermore, the reaction temperature is at least 80 °C. The application of cationic rhodium(I) solvate complexes (that no longer contain blocking diolefins) shows that a much greater activity and enantioselectivity for the synthesis of 1,2‐dihydro‐1‐naphthols can be reached than was described so far, even at ambient temperature. NMR spectroscopy and X‐ray analysis show that a product inhibition during the ring opening reaction takes place that is independent of the nucleophile.