37471-46-8

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 93-55-0 1-phenyl-propan-1-one 
• 51666-96-7 1-phenyl-2-(trimethylsilyl)-2-propen-1-ol 
• 400-53-3 trimethylsilyl trifluoroacetate 
• 7449-74-3 N-methyl-N-trimethylsilylacetamide 
• 39623-95-5 1-phenylprop-1-enyl acetate 
• 49750-22-3 1-(trimethylsilyl)vinylmagnesium bromide 
• 100-52-7 benzaldehyde 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 98-86-2 acetophenone 
• 18107-18-1 diazomethyl-trimethyl-silane 

Downstream Products

• 33513-50-7 (±)2-methyl-1,3-diphenylbutane-1-one 
• 66324-04-7 2,2-Dichloro-4-methyl-3-phenyl-3-trimethylsilanyloxy-cyclobutanone 
• 89318-24-1 4-(1-Methyl-2-oxo-2-phenyl-ethyl)-4H-pyridine-1-carboxylic acid 2,2,2-trichloro-ethyl ester 
• 109853-27-2 2-(2-Hydroxy-1,2,3,4-tetrahydro-pyrimidin-4-yl)-1-phenyl-propan-1-one 
• 6493-83-0 2-methoxy-1-phenyl-propan-1-one 
• 137502-11-5 4-(1-benzoylethyl)-2,3-dichloro-4-hydroxycyclobut-2-enone 
• 105619-05-4 1,3-bis(methoxycarbonyl)-4-(1-methyl-2-oxo-2-phenylethyl)-1,4-dihydropyridine 
• 16735-22-1 3-hydroxy-2-methylpropiophenone 
• 107994-99-0 (R)-3-((S)-1-Methyl-2-oxo-2-phenyl-ethyl)-cyclohexanone 
• 107994-99-0 (R)-3-((R)-1-Methyl-2-oxo-2-phenyl-ethyl)-cyclohexanone 
• 129139-66-8 3-(1-Methyl-2-oxo-2-phenyl-ethyl)-cyclohexanone 
• 55991-71-4 4-Methyl-5-phenyl-2,3-dihydrofuran-2,3-dione 
• 28403-86-3 1-phenyl-2-(phenylthio)propan-1-one 
• 56011-31-5 3-bromo-2-methyl-1-phenylpropan-1-one 

Relevant academic research and scientific papers

Borane-Catalyzed Direct Asymmetric Vinylogous Mannich Reactions of Acyclic α,β-Unsaturated Ketones

Herein, we report that, by using chiral bicyclic bisborane catalysts, we have achieved the first highly regio-, diastereo-, and enantioselective direct asymmetric vinylogous Mannich reactions of acyclic α,β-unsaturated ketones. The strong Lewis acidity and steric bulk of the bisborane catalysts were essential for the observed high yields and selectivities.

1,2-Carbopentafluorophenylation of Alkynes: The Metallomimetic Pull-Push Reactivity of Tris(pentafluorophenyl)borane

We report the novel single-step 1,2-dicarbofunctionalization of an arylacetylene with an allylsilane and tris(pentafluorophenyl)borane [B(C6F5)3] involving C?C bond formation with C?H bond scission at the β-position to the silicon atom of an allylsilane and B→C migration of a C6F5 group. The 1,2-carbopentafluorophenylation occurs smoothly without the requirement for a catalyst or heating. Mechanistic studies suggest that the metallomimetic “pull-push” reactivity of B(C6F5)3 imparts consecutive electrophilic and nucleophilic characteristics to the benzylic carbon of the arylacetylene. Subsequent photochemical 6π-electrocyclization affords tetrafluoronaphthalenes, which are important in the pharmaceutical and materials sciences. Owing to the unique reactivity of B(C6F5)3, the 1,2-carbopentafluorophenylation using 2-substituted furan proceeded with ring opening, and the reaction using silyl enolates formed a C?C bond with C?O bond scission at the silyloxy-substituted carbon.

Three-Component Coupling of Acyl Fluorides, Silyl Enol Ethers, and Alkynes by P(III)/P(V) Catalysis

We report herein on the phosphine-catalyzed hydrovinylation reaction by three-component coupling of acyl fluorides, silyl enol ethers, and alkynoates. The key to the success of the reaction is the formal transmetalation between pentacoordinate P(V) species (i.e., fluorophosphorane) and a silyl enol ether, which allows for C-C bond formation between the polarity-mismatched sites. The bond formation that cannot be attained even by transition metal catalysis is accomplished by a P(III)/P(V) manifold.

Photocatalytic Stoichiometric Oxidant-Free Synthesis of Linear Unsaturated Ketones from 1,2-Disubstituted Cyclopropanols

A one-step catalytic oxidant-free synthesis of unsaturated ketones from 1,2-disubstituted cyclopropanols is reported. Previously for this transformation, only two- and three-step protocols have been developed. The reaction proceeds under irradiation with visible light in the presence of catalytic amounts of both an acridinium photocatalyst and a cobaloxime complex. 2-Aryl-substituted cyclopropanols react giving α,β-unsaturated ketones, while dehydrogenative ring opening of 2-alkyl-substituted substrates affords mixtures of α,β- and β,γ-enones. The reaction starts with one-electron oxidation of a cyclopropanol to cyclopropyloxy radical, presumably, by the photoexcited acridinium catalyst. We also found that Co(dmgBF 2) 2(MeCN) 2complex under an air atmosphere and irradiation with blue LEDs or upon heating can serve as a hydroxycyclopropane oxidant.

Electrochemical, Iodine-Mediated α-CH Amination of Ketones by Umpolung of Silyl Enol Ethers

The electrochemical, oxidative Umpolung reaction of silyl enol ethers utilizing simple iodide salts for the synthesis of α-amino ketones is described. The products were isolated in excellent yields of up to 100percent, and various functionalized starting materials were accepted in an undivided electrochemical cell design. Moreover, a sensitivity assessment to ensure an improved reproducibility of the reaction and cyclic voltammetry experiments were performed to postulate a plausible reaction mechanism on their basis.

C?O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non-Rubottom Oxidation

Malonyl peroxides act both as oxidants and reagents for C?O coupling in reactions with methyl and silyl enol ethers. In the proposed conditions, the oxidative C?O coupling of malonyl peroxides with enol ethers selectively proceeds, bypassing the traditional Rubottom hydroxylation of enol ethers by peroxides. It was observed that the oxidative [5+2] cycloaddition of malonyl peroxides and enol ethers is the key stage of the discovered process. Oxidative C?O coupling of silyl enol ethers leads to the formation of α-acyloxyketones with a free carboxylic acid group. A specially developed preparative one-pot procedure transforms ketones via silyl enol ethers formation and the following coupling into α-acyloxyketones with yields 35–88%. The acid-catalyzed coupling with methyl enol ethers gives remarkable products while retaining the easily oxidizable enol fragment. Furthermore, these molecules contain a free carboxylic acid group, thus these nontrivial products contain two usually incompatible acid and enol ether groups. (Figure presented.).

Alkyl Ethers as Traceless Hydride Donors in Br?nsted Acid Catalyzed Intramolecular Hydrogen Atom Transfer

A new protocol for the deoxygenation of alcohols and the hydrogenation of alkenes under Br?nsted acid catalysis has been developed. The method is based on the use of either a benzyl or isopropyl ether as a traceless hydrogen-atom donor, and involves an intramolecular hydride transfer as a key step, which is achieved in a regio- and stereoselective manner.

Enantioselective N-Heterocyclic Carbene Catalyzed Synthesis of Functionalized Indenes

An enantioselective NHC (N-heterocyclic carbene) catalyzed synthesis of indenes from bifunctional α,β-unsaturated acyl fluorides and TMS enol ethers has been discovered. The reaction has broad generality (31 examples) and proceeds with high levels of enantioselectivity (most >92:8 er). Mechanistically the reaction likely occurs via a Michael/β-lactonization/decarboxylation sequence. Derivatization studies and limitations are discussed.

Tying a Molecular Overhand Knot of Single Handedness and Asymmetric Catalysis with the Corresponding Pseudo-D3-Symmetric Trefoil Knot

We report the stereoselective synthesis of a left-handed trefoil knot from a tris(2,6-pyridinedicarboxamide) oligomer with six chiral centers using a lanthanide(III) ion template. The oligomer folds around the lanthanide ion to form an overhand knot complex of single handedness. Subsequent joining of the overhand knot end groups by ring-closing olefin metathesis affords a single enantiomer of the trefoil knot in 90% yield. The knot topology and handedness were confirmed by NMR spectroscopy, mass spectrometry, and X-ray crystallography. The pseudo-D3-symmetric knot was employed as an asymmetric catalyst in Mukaiyama aldol reactions, generating enantioselectivities of up to 83:17 er, which are significantly higher than those obtained with a comparable unknotted ligand complex.

Stereoselective Synthesis of Highly Substituted Tetrahydrofurans through Diverted Carbene O-H Insertion Reaction

Copper- or rhodium-catalyzed reactions of diazocarbonyl compounds with β-hydroxyketones give highly substituted tetrahydrofurans with excellent diastereoselectivity. Under mild conditions, the single-step process starts as a carbene O-H insertion reaction, but is diverted by an intramolecular aldol reaction. Gone astray: Copper- or rhodium-catalyzed reactions of diazocarbonyl compounds with β-hydroxyketones give highly substituted tetrahydrofurans with excellent diastereoselectivity. The single-step reaction proceeds under mild conditions, starting as a carbene O-H insertion reaction, but then diverting to an intramolecular aldol reaction.