18388-07-3Relevant articles and documents
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.
Synthesis of α-iodo-α,β-unsaturated ketones by the reaction of α- silyl-α,β-unsaturated ketones with ICl or ICIl-AlCl3
Alimardanov, Asaf,Negishi, Ei-ichi
, p. 3839 - 3842 (2007/10/03)
Treatment of α-silyl-α,β-unsaturated enones, readily preparable as regio- and stereodefined compounds in high yields, with either 2 equiv, of ICl or one equiv, each of ICl and AlCl3 provides the corresponding α-iodo- α,β-unsaturated enones in h
Acylsilenes (3-Oxo-1-sila-1-propenes) from Acyl(disilanyl)carbenes
Schneider, Klaus,Daucher, Birgit,Fronda, Antonio,Maas, Gerhard
, p. 589 - 594 (2007/10/02)
UV photolysis of diazo(disilanyl)methyl ketones 2 in benzene generates acyl(disilanyl)carbenes 3, which rearrange to 3-oxo-1-sila-1-propenes 4.The latter compounds are reactive intermediates which either cyclize to 1-oxa-2-sila-3-cyclobutenes 5 or form th
