37715-31-4Relevant articles and documents
A new concise synthesis of (+)-ipomeamarone, (-)-ngaione, and their stereoisomers
Usuki, Yoshinosuke,Deguchi, Taku,Iio, Hideo
, p. 1882 - 1884 (2014)
A new concise and enantiocontrolled total synthesis of (+)-ipomeamarone (1), a well-known phytoalexin, is described. The key step involved a tetrahydrofuran ring construction from optically active furyl alcohol 5 via the π-allyl palladium complex with a chiral phosphine ligand. This procedure was also applicable to the synthesis of (1)-ngaione (2) and its stereoisomers.
INTERACTION OF 6,7-EPOXYGERANYL ACETATE AND OF 10,11-EPOXY-(E,E)-FARNESYL ACETATE WITH FLUOROSULFONIC ACID
Ungur, N. D.,Popa, N. P.,Vlad, P. F.
, p. 613 - 617 (1993)
The interaction of 6,7-epoxygeranyl acetate and of 10,11-epoxy-(E,E)-farnesyl acetate with fluorosulfonic acid forms isomerization products and products of the opening of the epoxide rings.
Iridoid Sex Pheromone Biosynthesis in Aphids Mimics Iridoid-Producing Plants
Partridge, Suzanne J.,Withall, David M.,Caulfield, John C.,Pickett, John A.,Stockman, Robert A.,Oldham, Neil J.,Birkett, Michael A.
supporting information, p. 7231 - 7234 (2021/04/21)
Biosynthesis of (1R,4aS,7S,7aR)-nepetalactol (1) and (4aS,7S,7aR)-nepetalactone (2) in plants involves iridoid synthase (ISY), an atypical reductive cyclase that catalyses the reduction of 8-oxogeranial into the reactive enol of (S)-8-oxocitronellal, and cyclization of this enol intermediate, either non-enzymatically or by a nepetalactol-related short chain dehydrogenase enzyme (NEPS) that yields the nepetalactols. In this study, we investigated the biosynthesis in vivo of 1 and 2 in the pea aphid, Acyrthosiphon pisum, using a library of isotopically-labelled monoterpenoids as molecular probes. Topical application of deuterium-labelled probes synthesized from geraniol and nerol resulted in production of 2H4?lactol 1 and 2H4?lactone 2. However, deuterium incorporation was not evident using labelled probes synthesized from (S)-citronellol. These results suggest that iridoid biosynthesis in animals, specifically aphids, may follow a broadly similar route to that characterised for plants.
Total Synthesis of (±)-Leonuketal
Brimble, Margaret A.,Furkert, Daniel P.,Grant, Phillip S.
supporting information, (2020/11/18)
Leonuketal is an 8,9-seco-labdane terpenoid with a unique tetracyclic structure, owing to a diversity-generating biosynthetic C-C bond cleavage event. The first total synthesis of leonuketal is reported, featuring a Ti(III)-mediated reductive cyclization of an epoxy nitrile ether, an unusual ring-opening alkyne formation as part of an auxiliary ring strategy, and the previously undescribed Au(I)-catalyzed cyclization of a β-keto(enol)lactone to assemble the core spiroketal motif.
Dirhodium(II)-Mediated Alkene Epoxidation with Iodine(III) Oxidants
Nasrallah, Ali,Grelier, Gwendal,Lapuh, Maria Ivana,Duran, Fernando J.,Darses, Benjamin,Dauban, Philippe
supporting information, p. 5836 - 5842 (2018/11/24)
Dirhodium(II) complexes and iodine(III) oxidants have found useful applications in synthetic nitrene chemistry. In this study, the combination of the dirhodium(II) complex Rh2(tpa)4 (tpa = triphenylacetate) with the iodine(III) oxidant PhI(OPiv)2 is shown to promote the epoxidation of alkenes in the presence of 2 equivalents of water. The reaction can be applied to diversely substituted alkenes and the corresponding epoxides are isolated with yields of up to 90 %. A possible mechanism involves the dirhodium(II) complex as a Lewis acid species that would tune the oxidizing character of the iodine(III) reagent.
