456-03-1Relevant articles and documents
Iridium Complexes as Efficient Catalysts for Construction of α-Substituted Ketones via Hydrogen Borrowing of Alcohols in Water
Luo, Nianhua,Zhong, Yuhong,Wen, Huiling,Shui, Hongling,Luo, Renshi
, p. 1355 - 1364 (2021/03/03)
Ketones are of great importance in synthesis, biology, and pharmaceuticals. This paper reports an iridium complexes-catalyzed cross-coupling of alcohols via hydrogen borrowing, affording a series of α-alkylated ketones in high yield (86 %–95 %) and chemoselectivities (>99 : 1). This methodology has the advantages of low catalyst loading (0.1 mol%) and environmentally benign water as the solvent. Studies have shown the amount of base has a great impact on chemoselectivities. Meanwhile, deuteration experiments show water plays an important role in accelerating the reduction of the unsaturated ketones intermediates. Remarkably, a gram-scale experiment demonstrates this methodology of iridium-catalyzed cross-coupling of alcohols has potential application in the practical synthesis of α-alkylated ketones.
Method for preparing alpha-alkyl substituted ketone compound
-
Paragraph 0141-0148, (2020/12/29)
The invention relates to a method for preparing an alpha-alkyl substituted ketone compound, which comprises the following steps: preparing a primary alcohol compound and a secondary alcohol compound as raw materials, adding alkali; with a cyclic iridium complex as a catalyst and water as a reaction medium, heating and stirring the mixture and reacting for 10 to 24 hours under the protection of inert gas, and cooling a reaction product to room temperature after the reaction is finished; carrying out reduced pressure distillation and concentration to obtain a crude product, and carrying out column chromatography purification to obtain a series of alpha alkyl substituted ketone compounds. The method is simple to operate, available in raw materials, low in price, high in reaction efficiency and selectivity, good in adaptability to various functional groups and wide in substrate universality; since water is used as a reaction medium to meet the green and environment-friendly requirements, the method is environmentally friendly and is carried out at gram level, so that the potential of industrially synthesizing the alpha alkyl substituted ketone compound is achieved; therefore, The method has expanded application in the fields of medicines, organic synthesis and the like.
Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide
Miao, Chengxia,Li, Xiao-Xi,Lee, Yong-Min,Xia, Chungu,Wang, Yong,Nam, Wonwoo,Sun, Wei
, p. 7476 - 7482 (2017/10/30)
The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an α-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn-oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the α-CH bonds of R- and S-enantiomers by a chiral high-valent manganese-oxo complex, supporting the experimental result from the OKR of secondary alcohols.