Highly regio- and stereoselective hydrosilylation of β-fluoroalkylated α,β-unsaturated ketones

Ikeda, Natsumi; Konno, Tsutomu

doi:10.1016/j.jfluchem.2015.02.010

Cited by 13 publications

(5 citation statements)

References 64 publications

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“…The hydrosilylation of α,β-unsaturated carbonyl compounds provides the corresponding silyl enol ethers, which are widely used as important substrates in organic synthetic reactions such as Mukaiyama-aldol condensations. − The reactions of an acyclic α,β-unsaturated ketone ( 1a ) with triethylsilane ( 2a ) in the presence of SiO 2 -supported Pd or Au monometallic catalysts at 75 °C gave the corresponding silyl enol ether 3a in very low yields (Table , entries 1 and 2). In contrast, supported Pd–Au alloy catalysts gave 3a (Table , entries 3–8), and supported 1Pd3Au/SiO 2 showed the highest activity among the SiO 2 -supported catalysts (Table , entry 6).…”

Section: Resultsmentioning

confidence: 99%

Supported Palladium–Gold Alloy Catalysts for Efficient and Selective Hydrosilylation under Mild Conditions with Isolated Single Palladium Atoms in Alloy Nanoparticles as the Main Active Site

et al. 2017

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Supported Pd−Au alloy catalysts were developed for the highly efficient and selective hydrosilylation of α,β-unsaturated ketones and alkynes. The Pd/Au atomic ratio of the Pd−Au alloy and the supporting material affected the catalytic activity, and supported Pd−Au alloy nanoparticles with a low Pd/Au atomic ratio functioned as highly active heterogeneous catalysts under mild reaction conditions. Structural characterization of supported Pd−Au alloy catalysts by X-ray diffraction, X-ray absorption spectroscopy (XAS), and transmission electron microscopy revealed the formation of random Pd−Au alloy nanoparticles with a uniform size of around 3 nm on the support. Furthermore, XAS and X-ray photoelectron spectroscopy elucidated the charge transfer from Pd to Au and the formation of isolated single Pd atoms in random Pd−Au alloys with a low Pd/Au ratio, which enabled efficient hydrosilylation of a variety of substrates under mild reaction conditions.

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Section: Resultsmentioning

confidence: 99%

Supported Palladium–Gold Alloy Catalysts for Efficient and Selective Hydrosilylation under Mild Conditions with Isolated Single Palladium Atoms in Alloy Nanoparticles as the Main Active Site

et al. 2017

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“…GS-MS: m/z (I rel. , %): 318 [M] + (11), 201 (100), 165 (45), 83 (5). 2m-D2(1SR/2RS): 1 H NMR (500 MHz, CDCl 3 ) δ 7.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…These alkenes take part in many various transformations with nucleophiles . They react with aryl halides, organosilanes, organoboron, and organolithium compounds . CF 3 -alkenes participate in reactions with enamines, enolates, and terminal alkynes .…”

Section: Introductionmentioning

confidence: 99%

Friedel–Crafts Alkylation of Arenes with 2-Halogeno-2-CF₃-styrenes under Superacidic Conditions. Access to Trifluoromethylated Ethanes and Ethenes

et al. 2016

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The formation of the corresponding benzyl cations [ArHC(+)-CH(X)CF3] takes place under protonation of E-/Z-2-halogeno-2-CF3 styrenes [ArCH═C(X)CF3, X = F, Cl, Br] in superacids. The structures of these new electrophiles were studied by means of NMR and theoretical DFT calculations. According to these data, in the case of bromo derivatives, the formed cations, most probably, exist as cyclic bromonium ions; however, in the cases of chloro and fluoro derivatives, open forms are more preferable. Subsequent reaction of these benzyl cations with arenes proceeds as Friedel-Crafts alkylation to afford 1,1-diaryl-2-halo-3,3,3-trifluoropropanes [Ar(Ar')CH-CH(X)CF3] in high yields (up to 96%) as a mixture of two diastereomers. The prepared halogenopropanes were easily converted into the corresponding mixtures of E-/Z-trifluoromethylated diarylethenes [Ar(Ar')C═CCF3] (in yields up to 96%) by dehydrohalogenation with base (KOH or t-BuOK). The mechanism of elimination (E2 and Ecb) depends on the nature of the leaving group and reaction conditions.

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“…Moreover, the further Mukaiyama aldol reaction of benzaldehyde with the obtained silyl enol ether was found to be highly syn-selective (Scheme 35). [71] Due to the prevalence of the gem-difluoro group in the pharmaceutically active molecules, there has been a significant work done on the synthetic methodology to incorporate it into the organic framework. In addition, the defluorinative approach has recently gained importance due to the availability of trifluoromethyl group.…”

Section: Borylation At β-Positionmentioning

confidence: 99%

“…Moreover, the further Mukaiyama aldol reaction of benzaldehyde with the obtained silyl enol ether was found to be highly syn ‐selective (Scheme 35). [71] …”

Section: Conjugate Addition Reactions Of β‐Cf3 Enonementioning

confidence: 99%

β‐Trifluoromethyl α,β‐unsaturated Ketones: Efficient Building Blocks for Diverse Trifluoromethylated Molecules

Chaudhary¹,

Kulkarni²,

Saiyed³

et al. 2020

Adv Synth Catal

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The trifluoromethyl (CF 3) group is an advantageous structural motif in various biologically active molecules as well as materials, which is depicted by steadily increasing demand from the industries involved in drug discovery, agrochemicals and material development. β-trifluoromethyl α,βunsaturated carbonyl compounds constitute a very efficient building blocks as starting material in the synthesis of fluorinated molecules. Their usage for the synthesis of various heterocycles and organic molecules bearing stereogenic carbon containing CF 3 motif has received significant attention during the recent times. This review provides the existing methods for the synthesis of β-substituted trifluoromethyl-α,β-unsaturated ketones and the efforts made by researchers for the synthetic development through various reactions by employing them as synthetic building blocks for trifluoromethylated organic scaffolds.

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Highly regio- and stereoselective hydrosilylation of β-fluoroalkylated α,β-unsaturated ketones

Cited by 13 publications

References 64 publications

Supported Palladium–Gold Alloy Catalysts for Efficient and Selective Hydrosilylation under Mild Conditions with Isolated Single Palladium Atoms in Alloy Nanoparticles as the Main Active Site

Supported Palladium–Gold Alloy Catalysts for Efficient and Selective Hydrosilylation under Mild Conditions with Isolated Single Palladium Atoms in Alloy Nanoparticles as the Main Active Site

Friedel–Crafts Alkylation of Arenes with 2-Halogeno-2-CF₃-styrenes under Superacidic Conditions. Access to Trifluoromethylated Ethanes and Ethenes

β‐Trifluoromethyl α,β‐unsaturated Ketones: Efficient Building Blocks for Diverse Trifluoromethylated Molecules

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Highly regio- and stereoselective hydrosilylation of β-fluoroalkylated α,β-unsaturated ketones

Cited by 13 publications

References 64 publications

Supported Palladium–Gold Alloy Catalysts for Efficient and Selective Hydrosilylation under Mild Conditions with Isolated Single Palladium Atoms in Alloy Nanoparticles as the Main Active Site

Supported Palladium–Gold Alloy Catalysts for Efficient and Selective Hydrosilylation under Mild Conditions with Isolated Single Palladium Atoms in Alloy Nanoparticles as the Main Active Site

Friedel–Crafts Alkylation of Arenes with 2-Halogeno-2-CF3-styrenes under Superacidic Conditions. Access to Trifluoromethylated Ethanes and Ethenes

β‐Trifluoromethyl α,β‐unsaturated Ketones: Efficient Building Blocks for Diverse Trifluoromethylated Molecules

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Friedel–Crafts Alkylation of Arenes with 2-Halogeno-2-CF₃-styrenes under Superacidic Conditions. Access to Trifluoromethylated Ethanes and Ethenes