- Direct Access to α,β-Unsaturated Ketones via Rh/MgCl2-Mediated Acylation of Vinylsilanes
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We report herein the facile and practical construction of α,β-unsaturated ketones via rhodium-catalyzed direct acylation of vinylsilanes with readily available and abundant carboxylic acids. This protocol features access to a diverse array of synthetically useful functionalities with moderate to excellent yields. More importantly, the late-stage functionalization of pharmaceuticals was also realized with synthetically useful yield.
- Chen, Zi-Yan,Deng, Xue-Zu,Song, Yang,Xue, Fei,Yamane, Motoki,Yue, Yan-Ni
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p. 12693 - 12704
(2021/09/28)
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- Regioselective α-Deuteration of Michael Acceptors Mediated by Isopropylamine in D2O/AcOD
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Site-specific hydrogen/deuterium exchange is an important method to access deuterated compounds for chemical and biological studies. Herein is reported the first method for the regioselective α-deuteration of enals and enones. The transformation features D2O and AcOD as deuterium sources and amines as organocatalysts. The deuteration strategy is scalable and works on enals with a variety of substituted arene or heterocycle motifs as well as enones. The method has been applied to the synthesis of deuterated drug precursors.
- Landge, Vinod G.,Shrestha, Kendra K.,Grant, Aaron J.,Young, Michael C.
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supporting information
p. 9745 - 9750
(2020/12/21)
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- Acylation of Alkenes with the Aid of AlCl3 and 2,6-Dibromopyridine
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Friedel-Crafts-type acylation of alkenes with acyl chlorides has been successfully conducted with a wide substrate scope by the combined use of AlCl3 and 2,6-dibromopyridine. Trisubstituted alkenes afford allylketones or vinylketones depending on the presence or absence of hydrogen atom(s) at the β-position to the acylation site, while monosubstituted alkenes exclusively afford vinylketones.
- Tanaka, Shinya,Kunisawa, Tsukasa,Yoshii, Yuji,Hattori, Tetsutaro
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supporting information
p. 8509 - 8513
(2019/11/03)
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- Intermolecular scandium triflate-promoted nitrene-transfer [5 + 1] cycloadditions of vinylcyclopropanes
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Sc(OTf)3-promoted [5 + 1] cycloaddition of vinylcyclopropanes with PhINTs is reported, enabling the regioselective preparation of a range of 1,2,3,6-tetrahydropyridine scaffolds under mild conditions. This represents the second example of a [5
- Laudenschlager, Julie E.,Combee, Logan A.,Hilinski, Michael K.
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supporting information
p. 9413 - 9417
(2019/11/14)
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- Oxidative conversion of silyl enol ethers to α,β-unsaturated ketones employing oxoammonium salts
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The oxidative conversion of silyl enol ethers to α,β-unsaturated ketones using a less-hindered class of oxoammonium salts (AZADO +BF4-) is described. The reaction proceeds via the ene-like addition of oxoammonium salts to silyl enol ethers.
- Hayashi, Masaki,Shibuya, Masatoshi,Iwabuchi, Yoshiharu
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p. 154 - 157
(2012/02/16)
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- Carbonylative addition of arylboronic acids to terminal alkynes: A new catalytic access to α,β-unsaturated ketones
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The carbonylative addition of arylboronic acids to terminal alkynes under mild conditions affords (E)-α,β-unsaturated ketones with good yields. The reaction was achieved with chloro(1,5-cyclooctadiene)rhodium(I) dimer or chlorodicarbonylrhodium(I) dimer a
- Dheur, Julien,Sauthier, Mathieu,Castanet, Yves,Mortreux, Andre
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p. 2499 - 2506
(2008/09/19)
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- Amine-promoted, organocatalytic aziridination of enones
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(Chemical Equation Presented) A novel method is presented using N-N ylides (prepared by in situ amination of a tertiary amine) for the aziridination of a range of enone systems. The amine may be used sub-stoichiometrically, and promising levels of enantioselectivity are observed with quinine as promoter.
- Armstrong, Alan,Baxter, Carl A.,Lamont, Scott G.,Pape, Andrew R.,Wincewicz, Richard
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p. 351 - 353
(2007/10/03)
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- An efficient synthesis of (E)-α,β-unsaturated ketones and esters with total stereoselectivity by using chromium dichloride
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(E)-α,β-Unsaturated ketones 1 or esters 2 can be obtained with complete stereoselectivity by reaction of different 2-chloro-3-hydroxy ketones 3 or esters 4 and CrCl2. A comparative study of the results of synthesis of ketones 1 with CrCl2 or samarium is performed. A mechanism to explain both β-elimination reactions has been proposed.
- Concellón, José M.,Rodríguez-Solla, Humberto,Méjica, Carmen
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p. 3292 - 3300
(2007/10/03)
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- Synthesis of (E)-α,β-unsaturated ketones with total or high diastereoselectivity by using samarium diiodide or triiodide
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(E)-α,β-Unsaturated ketones are obtained by reaction of α-chloro-β-hydroxy ketones with samarium diiodide or with samarium triiodide with total or high diastereoselectivity and in good yield.
- Concellón, José M.,Huerta, Mónica
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p. 1931 - 1934
(2007/10/03)
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- Palladium-catalyzed coupling reaction of acylzirconocene chlorides with hypervalent iodonium salts: Synthesis of aryl-substituted ketones
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The palladium-catalyzed acylation reaction of alkenoyl- and alkanoylzirconocene chlorides with hypervalent iodonium salts afforded the acylated aromatic compounds under mild conditions.
- Kang, Suk-Ku,Yoon, Seok-Keun
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p. 459 - 461
(2007/10/03)
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- Rearrangement of allylic and propargylic alcohols catalyzed by the combined use of tetrabutylammonium perrhenate(VII) and p-toluenesulfonic acid
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Allylic rearrangement and/or dehydration reaction of allylic alcohols proceeds smoothly by the use of catalytic amounts of tetrabutylammonium perrhenate and p-toluenesulfonic acid hydrate. Treatment of propargylic alcohols with the catalysts at room temperature affords the rearranged products, α,β-unsaturated carbonyl compounds, while β,γ-unsaturated ketones are obtained as main products by the reaction in refluxing 1,2-dichloroethane. The application of this catalytic system is also described for the preparation of some synthetic intermediates.
- Narasaka,Kusama,Hayashi
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p. 2059 - 2068
(2007/10/02)
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- ISOMERAZATION OF PROPARGYLIC ALCOHOLS CATALYZED BY AN IRIDIUM COMPLEX
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α,β-Enones were synthesized by the isomerization of propargylic alcohols catalyzed by an iridium pentahydride complex.
- Ma, Dawei,Lu, Xiyan
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p. 2109 - 2112
(2007/10/02)
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- The First Example of a Catalytic Wittig-Type Reaction. Tri-n-butylarsine-Catalyzed Olefination in the Presence of Triphenyl Phosphite
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Tri-n-butylarsine-catalyzed olefination was achieved by the reaction of various aldehydes with methyl bromoacetate (or ω-bromoacetophenone) in the presence of triphenyl phosphite and potassium carbonate at room temperature in good yields with high E stereoselectivity.
- Shi, Lilan,Wang, Weibo,Wang, Yucheng,Huang, Yao-Zeng
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p. 2027 - 2028
(2007/10/02)
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- THE REACTION OF ORGANOMETALLIC REAGENTS WITH UNSYMMETRICALLY SUBSTITUTED VINAMIDINIUM AND CHLOROPROPENIMINIUM SALTS
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A variety of organometallic reagents have been found to undergo regioselective reaction with 1-aryl-vinamidinium salts and 3-aryl-3-chloropropeniminium salts.The products of such reactions were found to be α,β-unsaturated ketones and chlorovinyl amines, respectively.
- Gupton, John T.,Coury, Joe,Moebus, Martin,Fitzwater, Susan
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p. 1575 - 1586
(2007/10/02)
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- Enone Synthesis via Palladium Catalyzed Reductive Carbonylation of Terminal Acetylenes
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Aryl vinyl ketones are prepared by the reaction of aryl iodides and terminal acetylenes in the presence of a catalytic amount of PdCl2(PPh3)2, Cp2TiCl2 and a stoichiometric amount of Zn-Cu under an atmospheric pressure of carbon monoxide.
- Tamaru, Yoshinao,Ochiai, Hirofumi,Yoshida, Zen-ichi
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p. 3861 - 3864
(2007/10/02)
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- Additions of Carboxylic Acid Dianions to α,β-Unsaturated Carbonyl Compounds - Control of the 1,2-/1,4-Regioselectivity by Steric Substituent Effects
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Dilithium carboxylic acid dianions 1 attack α,β-unsaturated aldehydes (2) 1,2-regiospecifically with formation of the unsaturated β-hydroxy carboxylic acids 3/4.Additionally, the addition of the phenylacetate dianion 1a can be conducted to the threo-isomer with high selectivity by reversible reaction. - α,β-Enones (8) add 1 irreversibly in 1,2- and 1,4-position.Depending on the substitution pattern, the whole range from pure 1,2- to pure 1,4-adduct is covered.The influence of the 1-counterion M and of the solvent is significant; the 1,4-portion increases with the complexing effect of M and with the Lewis-basicity of the solvent.
- Mulzer, Johann,Bruentrup, Gisela,Hartz, Georg,Kuehl, Uwe,Blaschek, Ursula,Boehrer, Gerald
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p. 3701 - 3724
(2007/10/02)
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