140462-87-9

Upstream product

• 201230-82-2 carbon monoxide 
• 50555-04-9 cinnamyl benzoate 
• 557-20-0 diethylzinc 
• 1629-58-9 4-penten-3-one 
• 100-52-7 benzaldehyde 
• 122-78-1 phenylacetaldehyde 
• 2243-53-0 trans-styrylacetic acid 
• 925-90-6 ethylmagnesium bromide 

Downstream Products

• 57044-49-2 2-ethyl-5-phenylfuran 

Relevant academic research and scientific papers

Selective functionalization of a variety of hydrocarbon c(sp3)-h bonds initiated by Cp?W(NO)(CH2CMe3)(η3-CH2CHCHPh)

Cp?W(NO)(CH2CMe3)(η3-CH2CHCHPh) (1) effects C(sp3)-H activations of methane, ethane, propane, and n-butane exclusively at their terminal carbons and forms the corresponding Cp?W(NO)(alkyl)(η3-CH2- CHCHPh) complexes. It also activates (n-Bu)2O, 1-chloropropane, and Me4Si in a similar manner. Exposure of the Cp?W(NO)(alkyl)(η3-CH2CHCHPh) complexes to carbon monoxide results in initial 1,1-CO insertion into the newly formed tungsten-alkyl bonds and formation of the corresponding η1-acyl complexes, some of which can be isolated. Additional functionalization of the C-H activation products occurs upon exposure to CO under more forcing conditions. Such treatment produces η2-bound unsaturated-ketone complexes resulting from CO insertion into the W-alkyl σ bonds followed by cross-coupling of the η1-acyl and the η3-allyl ligands and coordination of CO at the resulting vacant coordination site at tungsten. The unsaturated ketones can be released from the metal's coordination spheres either by photolysis of the complexes in MeCN or by further exposure of them to CO. All new compounds have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of six of them have been established by single-crystal X-ray crystallographic analyses.

Controlling the α/γ-Reactivity of Vinylogous Ketone Enolates in Organocatalytic Enantioselective Michael Reactions

The first regio-, diastereo-, and enantioselective direct Michael reaction of β,γ-unsaturated ketones with nitroolefins is enabled by Br?nsted base/hydrogen-bonding bifunctional catalysis. A squaramide-substituted tertiary amine catalyzes the reaction of a broad range of β,γ-unsaturated ketones to proceed at the α-site exclusively, giving rise to adducts with two consecutive tertiary carbon stereocenters in diastereomeric ratios of up to >20:1 and enantioselectivities generally in the 90–98 % ee range.

Regioselective ring opening and isomerization reactions of 3,4-epoxyesters catalyzed by boron trifluoride

Efficient ring opening of 3,4-epoxyesters with alcohols to produce 4-alkoxy-3-hydroxyesters and their isomerization into 4-ketoesters using boron trifluoride as the catalyst are presented. Both transformations are simple and efficient methods for the synthesis of the above named synthetically useful compounds.

Indium-catalyzed cross-coupling reactions between α,β -unsaturated carbonyl compounds and aromatic aldehydes

Cross-coupling reactions between α,β-unsaturated carbonyl compounds and aromatic aldehydes have been achieved in tetrahydrofuran (THF) at 25 °C under N2 using a catalytic amount of InCl3 (0. 05 molar amount to the substrate) in the presence of both chlorotrimethylsilane (TMSCl) and aluminum foil (Al). These reactions provide the corresponding β,γ-unsaturated ketones in moderate yields, together with pinacol-coupling products of aldehydes as side products. Chlorides other than TMSCl and AlCl3, such as LiCl, CaCl2, MgCl2, and SOCl2, are not effective at all. Without either TMSCl or Al, no reaction proceeds even in the presence of the catalyst.

Unsymmetrical Ketone Synthesis via a Three-Component Connection Reaction of Organozincs, Allylating Agents, and Carbon Monoxide

A wide variety of organozincs (diethylzinc, alkylzinc halides, and organozincs 2, 5, and 9a-e, functionalized with ester and nitrile groups) undergo a three-component connection reaction with carbon monoxide and allylic benzoates or phosphates 1a-h to furnish unsymmetrical ketones, e.g., 3, 6, and 10, in good yields uder 1 atm of carbon monoxide at ambient temperature by the catalysis of tetrakis(triphenylphosphine)palladium in THF/HMPA.The regio- and stereoselectivities of the present carbonylation show marked contrast to those reported for the palladium-catalyzed carbonylation of usymmetrical allylic substrates.For example, the reaction of crotyl benzoate with octylzinc iodide provides all the possible stereo- and regioisomers, i.e., cis- and trans-2-butenyl and 1-methyl-2-propenyl octyl ketones in comparable amounts.The carbonylative coupling of carvyl phosphates, trans- and cis-1h, and γ-zincio ester 5 is stereospecific and proceeds with inversion of configuration at the allylic stereocenters to furnish cis- and trans-6h, respectively, as single diastereomers.In the absence of HMPA, the reaction feature changes dramatically and lactones 12 and 13 (composed of organozincs, carbon monoxide, and allylating agents in the ratios of 1:1:2 and 2:1:1, respectively) and symmetrical keto diesters 14 (composed of 2 mol of organozincs and 1 mol of carbon monoxide) are formed in varying ratios depending on the reaction conditions.Synthetic scope of the unsymmetrical ketones and mechanistic rationale for these unique and unprecedented reaction behaviors are discussed.