om200788p_si_004.cif (21.08 kB)
Mild and Selective C(CO)–C(α) Bond Cleavage of Ketones by Rhodium(III) Porphyrins: Scope and Mechanism
dataset
posted on 2012-01-23, 00:00 authored by Hong Sang Fung, Bao Zhu Li, Kin Shing ChanRhodium(III) porphyrins were found to undergo selective
C(CO)–C(α)
bond activation (CCA) of ketones promoted by water at temperatures
as low as 50 °C. The acyl group of the ketone was transferred
to the rhodium center, and the alkyl fragment was oxidized to a carbonyl
moiety accordingly. The hydroxyl group of water is transferred to
the rhodium porphyrin through hydrolysis of the kinetic α-carbon–hydrogen
bond activation (α-CHA) product to give RhIII(ttp)OH
(ttp = 5,10,15,20-tetratolylporphyrinato dianion), which subsequently
cleaves the C(CO)–C(α) bond of ketone.