60507-03-1Relevant articles and documents
Mechanistic Difference in Photoreduction of Phenacyl Halides by NADH Model Compounds
Fukuzumi, Shunichi,Mochizuki, Seiji,Tanaka, Toshio
, p. 1983 - 1986 (1988)
Photoreduction of phenacyl halides by an NADH model compound, 10-methylacridan (AcrH2), in MeCN proceeds via photoinduced electron transfer from the singlet excited state of AcrH2 to phenacyl halides without the conribution of radical chain reactions, while the photoreduction by another NADH model compound, 1-benzyl-1,4-dihydronicotinamide (BNAH), proceeds via photoinduced radical chain reactions.The origin of the mechanistic difference between AcrH2 and BNAH has been discussed.
Synthesis method of alpha or beta-substituted aromatic ketone
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Paragraph 0022-0027; 0086-0090, (2021/05/01)
The invention discloses a synthesis method of alpha-or beta-substituted aromatic ketone. The method comprises the following steps: under the condition of inert gas, reacting alpha-oxo-aryl ethanone compounds, B2pin2, PDI-CoCl2 and MBHEt3 in an organic solvent at room temperature, then adding a compound 2, and continuously reacting to obtain a compound 3, wherein in the MBHEt3, M is an alkali metal; the compound 2 is selected from the group consisting of deuterated methanol, Selectfluoro, a TogniII reagent or R2CHO; R2 is an aromatic substituent or alkyl; the organic solvent is an aprotic organic solvent. According to the method, the alpha-oxo aryl ethanone is used as a raw material, a cheap and stable boron reagent and an efficient cobalt catalyst which is cheap and easy to obtain are used, an activating reagent MBHEt3 is added to generate an enol boron ether intermediate, then the enol boron ether intermediate and different electrophilic reagents are synthesized into alpha-or beta-substituted aromatic ketone, the reaction is carried out at normal temperature, and the operation is convenient.
Water-Accelerated Nickel-Catalyzed α-Crotylation of Simple Ketones with 1,3-Butadiene under pH and Redox-Neutral Conditions
Chen, Tiantian,Dong, Guangbin,Xing, Dong,Yang, Haijian,Yang, Yang
, p. 4238 - 4243 (2020/05/05)
We report a nickel/NHC-catalyzed branched-selective α-crotylation of simple ketones using 1,3-butadiene as the alkylation agent. This reaction is regioselective and operated under pH and redox-neutral conditions. Water was used as the sole additive, which significantly accelerates the transformation.
Mechanism of Catalytic Oxidation of Styrenes with Hydrogen Peroxide in the Presence of Cationic Palladium(II) Complexes
Walker, Katherine L.,Dornan, Laura M.,Zare, Richard N.,Waymouth, Robert M.,Muldoon, Mark J.
, p. 12495 - 12503 (2017/09/23)
Kinetic studies, isotope labeling, and in situ high-resolution mass spectrometry are used to elucidate the mechanism for the catalytic oxidation of styrenes using aqueous hydrogen peroxide (H2O2) and the cationic palladium(II) compound, [(PBO)Pd(NCMe)2][OTf]2 (PBO = 2-(pyridin-2-yl)benzoxazole). Previous studies have shown that this reaction yields acetophenones with high selectivity. We find that H2O2 binds to Pd(II) followed by styrene binding to generate a Pd-alkylperoxide that liberates acetophenone by at least two competitive processes, one of which involves a palladium enolate intermediate that has not been previously observed in olefin oxidation reactions. We suggest that acetophenone is formed from the palladium enolate intermediate by protonation from H2O2. We replaced hydrogen peroxide with t-butyl hydroperoxide and found that, although the palladium enolate intermediate was observed, it was not on the major product-generating pathway, indicating that the form of the oxidant plays a key role in the reaction mechanism.
