58944-42-6Relevant articles and documents
Selectivity enhancement of epoxide hydrolase catalyzed resolution of 2,2-disubstituted oxiranes by substrate modification
Osprian, Ingrid,Stampfer, Wolfgang,Faber, Kurt
, p. 3779 - 3785 (2000)
A series of (+)-2,2-disubstituted oxiranes bearing an alkene or alkyne functional group were resolved by bacterial epoxide hydrolases with excellent selectivities. The presence of a carbon-carbon double or triple bond furnished a highly flexible system fo
An Alkyne-Metathesis-Based Approach to the Synthesis of the Anti-Malarial Macrodiolide Samroiyotmycin A
Fürstner, Alois,Grimes, Mark I.,Hulme, Alison N.,Whitelegge, James T.,Yiannakas, Ektoras
supporting information, p. 18504 - 18508 (2021/07/26)
We report the first total synthesis of samroiyotmycin A (1), a C2-symmetric 20-membered anti-malarial macrodiolide isolated from Streptomyces sp. The convergent synthetic strategy orchestrates bisalkyne fragment-assembly using an unprecedented Sch?llkopf-type condensation on a substituted β-lactone and an ambitious late-stage one-pot alkyne cross metathesis–ring-closing metathesis (ACM–RCAM) reaction. The demanding alkyne metathesis sequence is achieved using the latest generation of molybdenum alkylidynes endowed with a tripodal silanolate ligand framework. Subsequent conversion to the required E-alkenes uses contemporary hydrometallation chemistry catalysed by tetrameric cluster [{Cp*RuCl}4].
Synthesis of Highly Oxygenated Carbocycles by Stereoselective Coupling of Alkynes to 1,3- and 1,4-Dicarbonyl Systems
Kier, Matthew J.,Leon, Robert M.,O'Rourke, Natasha F.,Rheingold, Arnold L.,Micalizio, Glenn C.
supporting information, p. 12374 - 12377 (2017/09/23)
Densely substituted and highly oxygenated carbocycles are challenging targets for synthesis. In particular, those possessing numerous contiguous, fully substituted carbon atoms (i.e., tertiary alcohols and quaternary centers) are often not accessible in a direct fashion, necessitating the strategic decoupling of ring-formation from the establishment of functionality about the system. Here, we describe an approach to the construction of highly oxygenated mono-, di-, and polycyclic carbocycles from the reaction of disubstituted alkynes with β- or γ-dicarbonyl systems. These processes embrace a variant of metallacycle-mediated annulation chemistry where initial alkyne-carbonyl coupling is followed by a second, now intramolecular, stereoselective C-C bond-forming event. In addition to revealing the basic reactivity pattern in intermolecular settings, we demonstrate that this class of reactivity is quite powerful in a fully intramolecular context and, when terminated by a stereoselective oxidation process, can be used to generate polycyclic systems containing a fully substituted and highly oxygenated five-membered ring.
