57072-60-3Relevant academic research and scientific papers
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.
Trichodiene Synthase. Synergistic Inhibition by Inorganic Pyrophosphate and Aza Analogs of the Bisabolyl Cation
Cane, David E.,Yang, Guohan,Coates, Robert M.,Pyun, Hyung-Jung,Hohn, Thomas M.
, p. 3454 - 3462 (2007/10/02)
A series of aza analogs of the bisabolyl and α-terpinyl cations were tested as inhibitors of the sesquiterpene cyclase, trichodiene synthase.Both (R)- and (S)-16 and (R)- and (S)-13 as well as trimethylamine were only weak inhibitors when incubated alone.In the presence of inorganic pyrophosphate, itself a known competitive inhibitor of trichodiene synthase, all five amines showed strong cooperative competitive inhibition with an enhancement factor estimated to be 10-40.The apparent induced inhibition constant αKJ decreased in going from trimethylamine to the monoterpene analogs 13 and was strongest for the sesquiterpene analogs 16, indicating that both electrostatic and hydrophobic interactions are important in the binding of each intermediate analog.The cyclase showed little discrimination, however, between the individual enantiomers of each inhibitor.
Identification and Synthesis of (Z)-(1'S,3'R,4'S)(-)-2-(3',4'-Epoxy-4'-methylcyclohexyl)-6-methylhepta-2,5-diene, the Sex Pheromone of the Southern Green Stinkbug, Nezara viridula (L.)
Baker, Raymond,Borges, Miguel,Cooke, Nigel G.,Herbert, Richard H.
, p. 414 - 416 (2007/10/02)
The sex pheromone of the male green stinkbug, Nezera viridula (L.) has been shown to be a novel epoxybisabolene (Z)-(1'S,3'R,4'S)(-)-2-(3',4'-epoxy-4'-methylcyclohexyl)6-methylhepta-2,5-diene, whose structure has been confirmed by spectroscopic studies and synthesis of the eight possible stereoisomers.
