84787-39-3Relevant academic research and scientific papers
Heavier Carbonyl Olefination: The Sila-Wittig Reaction
Reiter, Dominik,Frisch, Philipp,Szilvási, Tibor,Inoue, Shigeyoshi
, p. 16991 - 16996 (2019)
The Wittig reaction is one of the most versatile tools in the repertoire of organic chemists. Thus, a broad variety of carbonyl compounds can be converted to tailor-made alkenes with phosphorus ylides under mild conditions. However, no comparable reaction has been reported for silanones, the silicon congeners of ketones. Here, we demonstrate for the first time the successful application of the Wittig olefination to iminosilylsilanone 1. The selective formation of a series of silenes (R2Sia? CR2) via the sila-Wittig reaction revealed an unprecedented approach to otherwise elusive compounds. In addition, the highly reactive and zwitterionic nature of 1 was also susceptible to nucleophilic attacks and cycloaddition reactions by and with the phosphorus ylides. Our results therefore make another important contribution to discovering the differences and similarities between carbon and silicon.
Cryptophycin compounds
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Page/Page column 149, (2010/02/05)
The present invention provides cryptophycin compounds of Formula I that are useful in the treatment of neoplasms.
NOUVELLE SYNTHESE DE TRIFLUOROMETHYLCETONES ET D' α-BROMO TRIFLUOROMETHYLCETONES
Begue, J. P.,Mesureur, D.
, p. 271 - 282 (2007/10/02)
We report a new method for the preparation of trifluoromethylketones, as an alternative to the use of organometallics.The condensation of phosphonium ylides with trimethylsilyl trifluoroacetate provides silyloxy enol ethers whose hydrolysis leads to trifluoromethylketones.Bromation of the same silyloxy enol ether is also a convenient preparation of α-bromo trifluoromethylketone.
Reactions of Allylidenephosphoranes with Heterocumulenes, II. New Syntheses of 1,2,4-Pentatrienes and 2-Pentene-1,5-diones
Capuano, Lilly,Wamprecht, Christian,Willmes, Arnold
, p. 3904 - 3907 (2007/10/02)
Cinnamylidenetriphenylphosphorane (2a) undergoes Wittig reaction with ketenes to afford monomeric and dimeric 1,2,4-pentatrienes 4 and 5, resp. 4b reacts further with an excess of ketene via a -cycloaddition, whereby the 3-styryl-1-naphthyl diphenylacetate 12 is formed.In contrast, with the α-phenylsubstituted phosphorane 2b, instead of the Wittig reaction addition of ketene takes place at both the α- and the γ-positions.The 1,3-diacyl-3-triphenylphosphonio-1-propen-3-enolate 6 readily hydrolyzes to the 2-pentene-1,5-dione 9.
Electro-organic Reactions. Part 17. The Competition between Cleavage and Ylid Formation in the Cathodic Reduction of Benzyl-, Allyl-, Cinnamyl-, and Polyenyl-phosphonium Salts
Pardini, Vera L.,Roullier, Loic,Utley, James H. P.,Webber, Andrew
, p. 1520 - 1524 (2007/10/02)
In aprotic solvents benzyl-, allyl-, cinnamyl-, and polyenyl-phosphonium salts undergo overall one-electron reduction with the formation of up to 50percent of the corresponding ylid.In cyclic voltammetric experiments peaks for the reduction of ylids have been clearly identified and the mechanism of formation is found to involve initial two-electron cleavage to a benzylic or allylic carbanion which abstracts proton from a second molecule of phosphonium salt.Benzyltriphenylphosphonium nitrate, in NN-dimethylformamide, is converted into the ylid by the dianion generated cathodically at -1.50 V (versus saturated calomel electrode) from dicyano(fluoren-9-ylidene)methane and in situ reaction with benzaldehyde gives stilbene in 74percent yield.Competitive electrolyses in acidic solution of p-methoxycarbonylbenzyltriphenylphosphonium and triethylammonium salts, and p-methoxycarbonylbenzyl naphthalene-1-carboxylate give for these two-electron cleavages a qualitative order of leaving group ability of Et3N > Ph3P >> RCO2-.
