3168-90-9Relevant articles and documents
Theoretical Study of Intramolecular Aldol Condensation of 1,6-Diketones: Trimethylsilyl Substituent Effect
Bouillon, Jean-Philippe,Portella, Charles,Bouquant, James,Humbel, Stephane
, p. 5823 - 5830 (2000)
Diastereoselective intramolecular aldol condensations are investigated in an experimental and computational study of 1,6-diketones. Ab initio results show the importance of the acid medium and disapprove the possibility of a spontaneous cyclization, even for silylated compounds. The combination of both experimental and computational approaches brings valuable information on the mechanism and on the selectivity of the aldol reaction. It is found that the enolization of the diketone is a key step in acid-catalyzed mechanism. The cyclization step bears a very small activation energy. The dehydration of the aldols are discussed.
(Trimethylsilyl)cyclopentene Annulation: A Regiocontrolled Approach to the Synthesis of Five-Membered Rings
Danheiser, Rick L.,Carini, David J.,Basak, Ajoy
, p. 1604 - 1606 (1981)
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Iridium complex-catalyzed addition of water and alcohols to non-activated terminal alkynes
Hirabayashi, Tomotaka,Okimoto, Yoshio,Saito, Akiyo,Morita, Masao,Sakaguchi, Satoshi,Ishii, Yasutaka
, p. 2231 - 2234 (2007/10/03)
The addition of water and alcohols to non-activated terminal alkynes was found to be promoted by an iridium complex combined with Lewis acid and phosphite. Thus, terminal alkynes reacted with water or alcohols to give ketones or ketals, respectively, in good to excellent yields. α,ω-Diyne like 1,7-octadiyne was converted into 1-(2-methyl-cyclopent-1-enyl)ethanone through the intramoleculer aldol condensation of the resulting 2,7-octanedione induced by Lewis acid.
Hydration of Alkynes in Anhydrous Medium with Formic Acis as Water Donor
Menashe, Naim,Shvo, Youval
, p. 7434 - 7439 (2007/10/02)
Formic acid has been found to hydrate alkynes in the absence of water to give oxo products and carbon monoxide.The scope of the reaction of alkynes and formic acid has been delineated.Hydrocarbon alkynes were found to be reactive in the absence of catalyst.Functionalized alkynes, in particular oxygenated alkynes, are inert toward formic acid but can be activated catalytically with Ru3(CO)12.Consequently, all the tested types of alkynes were found to give oxo products and CO with formic acid.The mechanism of the reaction was examined.With some alkynes, the primary oxo products underwent secondary reactions that gave rise to unexpected products.