6090-09-1Relevant articles and documents
Lutz,Bailey
, p. 3899 (1964)
Viable route and DFT study for the synthesis of optically active limonaketone: A barely available natural feedstock in Cedrus atlantica
Mekkaoui, Ayoub Abdelkader,Ben El Ayouchia, Hicham,Anane, Hafid,Chahboun, Rachid,El Firdoussi, Larbi,El Houssame, Soufiane
, (2021/03/24)
Herein, we report a novel, easy and efficient synthesis pathway of optically active limonaketone, a high added value monoterpene, starting from limonene, natural and low-cost feedstock. The strategy was developed in an excellent three-step total synthesis of limonaketone, potentially important intermediate in limonene ozonolysis and barely available in Cedrus atlantica essential oil (0.1% yield). The first step was the epoxidation of limonene which proceed in 91% yield. The ozonolysis of the prepared limonene oxide leads to the formation of the characteristic ketone function of limonaketone in 92% yield. The last step was performed by a deoxygenation in the presence of Zn and gave limonaketone in quantitative yield. The optically pure limonaketone has been efficiently synthesized from limonene and the overall yield was 84%. A molecular electron density theory (MEDT) analysis was carried out by using density functional theory (DFT) calculations at the M06–2X/6–311G(d,p) (LANL2DZ for Zn) level to understand the observed chemoselectivity in the Zn-deoxygenation reaction as well as its corresponding mechanistic pathway.
Identification of the early intermediates formed in ozonolysis of: Cis-2-butene and limonene: A theoretical and matrix isolation study
Li, Shan-Shan,Yang, Xiao-Yang,Xu, Yi-Sheng,Jiang, Lei
, p. 20100 - 20106 (2019/07/09)
This study combined quantum chemical calculations and the matrix isolation technique to identify the formation of primary intermediates from the ozonolysis of cis-2-butene and limonene. Quantum chemical calculations were conducted under the framework of density functional theory (DFT) at M06-2x/6-311+(d, p) level of theory to predict the possible mechanism as well as the new absorption bands. New bands whose intensity increased with annealing, were observed in twin jet deposition, which indicated the formation of primary ozonides, CI and secondary ozonides in the investigated systems. Isotopic labeling (18O) experiments further supported the assignment of observed bands. The results and findings in this study would enrich the understanding of the reaction mechanism of alkene ozonolysis.
