4571-02-2Relevant articles and documents
1,5,7-Triazabicyclo[4.4.0]dec-5-ene Enhances Activity of Peroxide Intermediates in Phosphine-Free α-Hydroxylation of Ketones
Wang, Yongtao,Lu, Rui,Yao, Jia,Li, Haoran
supporting information, p. 6631 - 6638 (2021/02/05)
The critical role of double hydrogen bonds was addressed for the aerobic α-hydroxylation of ketones catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), in the absence of either a metal catalyst or phosphine reductant. Experimental and theoretical investigations were performed to study the mechanism. In addition to initiating the reaction by proton abstraction, a more important role of TBD was revealed, that is, to enhance the oxidizing ability of peroxide intermediates, allowing DMSO to be used rather than commonly used phosphine reductants. Further characterizations with nuclear Overhauser effect spectroscopy (NOESY) confirmed the presence of double hydrogen bonds between TBD and the ketone, and kinetic studies suggested the attack of dioxygen on the TBD-enol adduct to be the rate-determining step. This work should encourage the application of TBD as a catalyst for oxidations.
A novel lanthanum metal-assisted reaction of diaryl ketones and electrophiles
Umeda, Rui,Ninomiya, Masashi,Nishino, Toshiaki,Kishida, Makoto,Toiya, Shunsuke,Saito, Tomoki,Nishiyama, Yutaka,Sonoda, Noboru
, p. 1287 - 1291 (2015/03/05)
A novel and efficient lanthanum metal-assisted carbon-carbon bond formation of diaryl ketones and various electrophiles, such as carbonyl compounds, esters, nitriles, and epoxides, has been developed. When diaryl ketones were allowed to react with dialkyl ketones in the presence of lanthanum metal and a catalytic amount of iodine, the cross pinacol coupling reaction proceeded to give the corresponding unsymmetrical 1,2-diols in moderate to good yields. α-Hydroxy ketones were prepared by the lanthanum metal-assisted reaction of diaryl ketones with esters or nitriles, followed by hydrolysis with aq HCl. It is interesting to note that for the epoxides, the coupling reaction proceeded via the Meinwald rearrangement of epoxides to give the corresponding 1,2-diols.
Aerobic oxygenation of benzylic ketones promoted by a gold nanocluster catalyst
Sakurai, Hidehiro,Kamiya, Ikuyo,Kitahara, Hiroaki,Tsunoyama, Hironori,Tsukudad, Tatsuya
experimental part, p. 245 - 248 (2009/06/23)
Gold nanoclusters stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP) promote the oxidation of benzylic ketones, including auto-oxidation-type bond-cleavage reactions and α-hydroxylation, under ambient conditions. The catalyst accelerates the formation of
