Ruthenium-Catalyzed Monoalkenylation of Aromatic Ketones by Cleavage of Carbon-Heteroatom Bonds with Unconventional Chemoselectivity

Ruthenium‐catalyzed selective monoalkenylation of ortho CO or CN bonds of aromatic ketones was achieved. The reaction allowed the direct comparison of the relative reactivities of the cleavage of different carbon‐heteroatom bonds, thus suggesting an unconventional chemoselectivity, where smaller,...

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Bibliographic Details
Published in:Angewandte Chemie 2015-08, Vol.127 (32), p.9425-9429
Main Authors: Kondo, Hikaru, Akiba, Nana, Kochi, Takuya, Kakiuchi, Fumitoshi
Format: Article
Language:eng ; ger
Subjects:
Bor
Chemical bonds
Chemistry
Chemoselektivität
Cleavage
Ketones
Ruthenium
Substituenteneffekte
Synthesemethoden
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Summary:Ruthenium‐catalyzed selective monoalkenylation of ortho CO or CN bonds of aromatic ketones was achieved. The reaction allowed the direct comparison of the relative reactivities of the cleavage of different carbon‐heteroatom bonds, thus suggesting an unconventional chemoselectivity, where smaller, more‐electron‐donating groups are more easily cleaved. Selective monofunctionalization of CO bonds in the presence of ortho CH bonds was also achieved. Kleiner ist besser: Die Titelreaktion ermöglicht die Spaltung von ortho‐C‐O‐ und ortho‐C‐N‐Bindungen in aromatischen Ketonen. Ein direkter Vergleich der Spaltung der Kohlenstoff‐Heteroatom‐Bindungen weist auf eine ungewöhnliche Selektivität hin, wonach kleinere, stärker elektronenschiebende Gruppen leichter abgespalten werden. Eine selektive Monofunktionalisierung von C‐O‐Bindungen in Anwesenheit von ortho‐C‐H‐Bindungen gelang ebenfalls.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201503641