50639-00-4Relevant articles and documents
Electronic and steric factors for enhanced selective synthesis of 2-ethyl-1-hexanol in the Ir-complex-catalyzed Guerbet reaction of 1-butanol
Xu, Zhanwei,Yan, Peifang,Liang, Changhui,Jia, Songyan,Liu, Xiumei,Zhang, Z. Conrad
, p. 1586 - 1592 (2021/05/10)
1-Butanol is a potential bio-based fermentation product obtained from cellulosic biomass. As a value-added chemical, 2-ethyl-1-hexanol (2-EH) can be produced by Guerbet conversion from 1-butanol. This work reports the enhanced catalytic Guerbet reaction of 1-butanol to 2-EH by a series of Cp*Ir complexes (Cp*: 1,2,3,4,5-pentamethylcyclopenta-1,3-diene) coordinated to bipyridine-type ligands bearing an ortho-hydroxypyridine group with an electron-donating group and a Cl? anion. The catalytic activity of the Cp*Ir complex increased by increasing the electron density of the bipyridine ligand when functionalized with the para-NMe2 and ortho-hydroxypyridine groups. A record turnover number of 14047 was attained. A mechanistic study indicated that the steric effect of the ethyl group on the α-C of 2-ethylhexanal (2-EHA) and the conjugation effect of C=C–C=O in 2-ethylhex-2-enal (2-EEA) benefits the high selectivity of 2-EH from 1-butanol by inhibiting the cross-aldol reaction of 2-EHA and 2-EEA with butyraldehyde. Nuclear magnetic resonance study revealed the formation of a carbonyl group in the bipyridine-type ligand via the reaction of the Cp*Ir complex with KOH.
Method for synthesizing unsaturated primary alcohol
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Paragraph 0079-0083, (2019/08/20)
The invention discloses a method for synthesizing an unsaturated primary alcohol. The method comprises the following steps: adding an unsaturated aldehyde, a transition metal catalyst iridium complexand isopropyl alcohol in a reaction container, heating the reaction mixture in an oil bath, carrying out a reaction for a plurality of hours, then carrying out cooling to room temperature, removing the solvent by rotating evaporation, and then carrying out column separation to obtain the target compound. According to the invention, the unsaturated aldehyde is used as a raw material, isopropyl alcohol is used as a hydrogen source and the solvent, and the unsaturated primary alcohol is generated through hydrogen transfer under participation of the transition metal iridium catalyst. The method has the following remarkable advantages: 1) the reaction temperature is low; 2) cheap, safe and non-toxic isopropanol is used; 3) the catalyst usage amount is low, and reaction atom economy is high; and4) selectivity is good. Therefore, the method meets the requirements of green chemistry and has a wide development prospect.
Transfer Hydrogenation of Aldehydes and Ketones with Isopropanol under Neutral Conditions Catalyzed by a Metal-Ligand Bifunctional Catalyst [Cp?Ir(2,2′-bpyO)(H2O)]
Wang, Rongzhou,Tang, Yawen,Xu, Meng,Meng, Chong,Li, Feng
, p. 2274 - 2281 (2018/02/23)
A Cp?Ir complex bearing a functional bipyridonate ligand [Cp?Ir(2,2′-bpyO)(H2O)] was found to be a highly efficient and general catalyst for transfer hydrogenation of aldehydes and chemoselective transfer hydrogenation of unsaturated aldehydes with isopropanol under neutral conditions. It was noteworthy that many readily reducible or labile functional groups such as nitro, cyano, ester, and halide did not undergo any change under the reaction conditions. Furthermore, this catalytic system exhibited high activity for transfer hydrogenation of ketones with isopropanol. Notably, this research exhibited new potential of metal-ligand bifunctional catalysts for transfer hydrogenation.