18282-51-4Relevant articles and documents
Sisti,Sawinski
, p. 2746 (1976)
Hydrogenation of Esters by Manganese Catalysts
Li, Fu,Li, Xiao-Gen,Xiao, Li-Jun,Xie, Jian-Hua,Xu, Yue,Zhou, Qi-Lin
, (2022/01/13)
The hydrogenation of esters catalyzed by a manganese complex of phosphine-aminopyridine ligand was developed. Using this protocol, a variety of (hetero)aromatic and aliphatic carboxylates including biomass-derived esters and lactones were hydrogenated to primary alcohols with 63–98% yields. The manganese catalyst was found to be active for the hydrogenation of methyl benzoate, providing benzyl alcohol with turnover numbers (TON) as high as 45,000. Investigation of catalyst intermediates indicated that the amido manganese complex was the active catalyst species for the reaction. (Figure presented.).
Hydroboration Reaction and Mechanism of Carboxylic Acids using NaNH2(BH3)2, a Hydroboration Reagent with Reducing Capability between NaBH4and LiAlH4
Wang, Jin,Ju, Ming-Yue,Wang, Xinghua,Ma, Yan-Na,Wei, Donghui,Chen, Xuenian
, p. 5305 - 5316 (2021/04/12)
Hydroboration reactions of carboxylic acids using sodium aminodiboranate (NaNH2[BH3]2, NaADBH) to form primary alcohols were systematically investigated, and the reduction mechanism was elucidated experimentally and computationally. The transfer of hydride ions from B atoms to C atoms, the key step in the mechanism, was theoretically illustrated and supported by experimental results. The intermediates of NH2B2H5, PhCH= CHCOOBH2NH2BH3-, PhCH= CHCH2OBO, and the byproducts of BH4-, NH2BH2, and NH2BH3- were identified and characterized by 11B and 1H NMR. The reducing capacity of NaADBH was found between that of NaBH4 and LiAlH4. We have thus found that NaADBH is a promising reducing agent for hydroboration because of its stability and easy handling. These reactions exhibit excellent yields and good selectivity, therefore providing alternative synthetic approaches for the conversion of carboxylic acids to primary alcohols with a wide range of functional group tolerance.
Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) iron (II) hydride for hydrosilylation of aldehydes and ketones
Du, Xinyu,Qi, Xinghao,Li, Kai,Li, Xiaoyan,Sun, Hongjian,Fuhr, Olaf,Fenske, Dieter
, (2021/05/29)
A novel silylene supported iron hydride [Si, C]FeH (PMe3)3 (1) was synthesized by C (sp3)-H bond activation with zero-valent iron complex Fe (PMe3)4. Complex 1 was fully characterized by spectroscopic methods and single crystal X-ray diffraction analysis. To the best of our knowledge, 1 is the first example of silylene-based hydrido chelate iron complex produced through activation of the C (sp3)?H bond. It was found that complex 1 exhibited excellent catalytic activity for hydrosilylation of aldehydes and ketones. The catalytic system showed good tolerance and catalytic activity for the substrates with different functional groups on the benzene ring. It is worth mentioning that, the experimental results showed that both ketones and aldehydes could be reduced in good to excellent yields under the same catalytic conditions. Based on the experiments and literature reports, a possible catalytic mechanism was proposed.
