Synthese asymetrique d'amines par hydrosilylation d'imines catalysee par un complexe chiral du rhodium

Mechanism of ketone hydrosilylation by Cu(I) catalysts: A theoretical study

“…1 Results (Table 2) show a consistent shift of about 5 kcal/mol for species involved in the transformation of the pre-catalyst to the catalyst, with respect to isolated reactants, and is due to a basis set superposition error involving the fluorine and silicon atoms. 2 This effect is no longer observed for the actual catalytic cycle (Tables 4 and 6). As the main objective of this paper is to study the plausibility of the actual catalytic cycle, with the possibility of transposing the basis set used to larger systems in order to study the enantioselectivity, the smaller basis set was chosen throughout this work.…”

“…It was not until the '70s, that the first Rh(I) based catalyst, used for reductive hydrosilylation of ketones and imines, yielding, respectively, alcohols and amines were developed [1][2][3]. The softer reaction conditions of hydrosilylation, turned out to be a major advantage over other reduction reactions, such as hydrogenation.…”

Improvements in the Total Synthesis of Morphine

“…2-Mesitylenesulfonyl chloride was purcohol (11, 68.3 g, 0.195 Thionyl chloride evaporation of the pyridine a solid product was obtained. Recrys-(6.2 g, 0.052 mol) was added dropwise to a solution of 3,5-dibenzyltallization from 160 mL of toluene gave methyl 3,5-diacetoxy-4-oxy-4-methoxybenzyl alcohol (11,10.5 g, 0.030 mol) in 80 mL of hydroxybenzoate (8, 158.4 g, 0.591 mol, 89%) as a white solid . The benzene.…”

“…Various 3,4,5,6,7,. [10] Two catalytic methods proved to be acceptably efficient for 1-benzyl-substi-[ ] Part 44: L. Maat, R. H. Woudenberg, G. J. Meuzelaar, J. T. M. Linders, Bioorg. Med.…”

Progress in Asymmetric Hydrosilylation of Ketones by Non-precious Metal Catalyst

“…经过多年研究和探索, 在潜手性酮的不对称催化方 面, 人们已经研发出了多种不对称硅氢加成反应金属催 化剂, 1973 年 Kagan 等 [8,9] 首次报道 Rh(I)/DIOP 催化潜 乙醚为溶剂, 室温下反应 1 h, 转化率最高可达到 99%, 光学选择性比较低, 最高只有 49%. 但 10a 与 B(C 6 F 5 ) 3 一起使用, 其光学选择性可达到 93%.…”