100765-40-0

Upstream product

• 591-78-6 n-hexan-2-one 
• 104-87-0 4-methyl-benzaldehyde 
• 903512-06-1 1-(4-methylphenyl)hept-2-ynyl acetate 
• 115085-22-8 1-(4-methylphenyl)-2-heptyn-1-ol 
• 70090-77-6 1-fluoro-4-(propa-1,2-dien-1-yl)benzene 
• 72316-17-7 (E)-2-(4-methylphenyl)ethenylboronic acid 

Relevant academic research and scientific papers

The synthesis and structural characterization of furanyl-1,2,3-triazole Gold(I) and its application in synthesis of enones from propargylic esters and alcohols

Furanyl-1,2,3-triazole gold(I) was designed, synthesized and characterized by X-ray crystallography, and was found to exhibit high catalytic activity for the synthesis of enones in good to high yields through a propargylic ester rearrangement and subsequent hydration. Notably, excellent E/Z selectivity was observed in these transformations. This catalyst was also effective in catalyzing the rearrangement of propargylic alcohols and hydration of alkynes. Compared to triazole acetyl gold(III) and other gold complexes, the furanyl-1,2,3-triazole gold(I) is able to promote these transformations smoothly at a low temperature with the E isomer of enones as the only product.

Pd-catalyzed Oxidative Cross-coupling of Alkyl Chromium(0) Fischer Carbene Complexes with Organoboronic Acids

Alkyl chromium(0) carbene complexes have been explored as the cross-coupling partners in the palladium-catalyzed reaction with aryl or alkenyl boronic acids. This coupling reaction displays the versatile reactivities of alkyl chromium(0) carbenes under palladium catalysis. Mechanistically, this transformation is proposed to involve deprotonation of the alkyl chromium carbene substrate to generate a vinyl chromium anion intermediate that undergoes transmetalation to organopalladium species and reductive elimination.

Triazole acetyl gold(III) catalyzed Meyer-Schuster rearrangement of propargyl alcohols

A new type triazole acetyl gold(III) was prepared and found to be an effective catalyst in Meyer-Schuster rearrangement of propargyl alcohols. The reactions proceeded well under much milder conditions to afford enones bearing a wide range of functional groups, thereby opening a new avenue for gold(III) catalysis. In addition, TriaAuCl2 catalyst was also effective on promotion of a-haloenones synthesis.

Preparation method of alpha-beta-unsaturated carbonyl compound

The invention relates to a preparation method of an alpha-beta-unsaturated carbonyl compound, in particular to a method in which the alpha-beta-unsaturated carbonyl compound is prepared from substitute propargyl alcohol in a mode that positive ion modified imvite serves as a catalyst, the substitute propargyl alcohol serves as the raw material, and Meyer-Schuster rearrangement is utilized. According to the method, the substrate is wide in application range, the catalyst is cheap, easy to manufacture, stable, free of pollution to the environment and capable of being recycled, the reaction yield is high, stereoselectivity is good, and an E-type product can be obtained in a singular mode.

Electrophilic addition of propargylic cations to allenes: Formation of crowded chloro- and azido-enynes by trapping of the resulting allylic cations with TMSX (X = Cl, N3): A synthetic and computational study

Propargylic cations, generated by the ionization of propargyl alcohols with catalytic amounts of Bi(OTf)3, react with aryl-substituted allenes to generate incipient allylic cations that are quenched in the presence of TMSCl to form a number of sterically crowded chloro-enynes as a mixture of Z and E isomers with a strong preference for the Z alkenes. Several other metallic triflates, M(OTf)3 (M = Sc, Yb, La), as well as bismuth nitrate Bi(NO3)3·5H2O also promote this reaction with similar conversions and stereoselectivity. Although trapping with TMSBr and TMSI gave intractable mixtures, trapping with TMSN3 in a couple of cases led to the isolation of the corresponding isomeric azido-enynes, albeit in lower isolated yields and lower stereoselectivity. Competitive formation of the Meyer-Schuster rearrangement products was also observed. Sterically crowded chloro-allenes did not form adducts with propargyl alcohols, instead they underwent a skeletal rearrangement under the influence of Bi(OTf)3 to form 2-chloro-butadienes. The results of DFT calculations indicated that the relative anti/syn energies of the propargyl cation and the energy difference between the Z/E isomeric products are too small to explain the stereochemical preference observed for the enynes. A study of the transition state in the crucial C-C bond-forming step by DFT indicated that rotation of the benzylic portion away from the propargyl cation may be a key factor in favoring the anti isomer of the allylic cation. Propargylic cations generated by the ionization of propargylic alcohols with metallic triflates react with aryl-allenes in the presence of TMSCl to form crowded chloro-enynes Copyright

Gold- and silver-catalyzed reactions of propargylic alcohols in the presence of protic additives

A wide range of primary, secondary and tertiary propargylic alcohols undergo a Meyer-Schuster rearrangement to give enones at room temperature in the presence of a gold(I) catalyst and small quantities of MeOH or 4-methoxyphenylboronic acid. The syntheses of the enone natural products isoegomaketone and daphenone were achieved using this reaction as the key step. The rearrangement of primary propargylic alcohols can readily be combined in a one-pot procedure with the addition of a nucleophile to the resulting terminal enone, to give β-aryl, β-alkoxy, β-amino or β-sulfido ketones. Propargylic alcohols bearing an adjacent electron-rich aryl group can also undergo silver-catalyzed substitution of the alcohol with oxygen, nitrogen and carbon nucleophiles. This latter reaction was initially observed with a batch of gold catalyst that was probably contaminated with small quantities of silver salt.

Triazole-gold-promoted, effective synthesis of enones from propargylic esters and alcohols: A catalyst offering chemoselectivity, acidity and ligand economy

The air, moisture and thermally stable 1,2,3-triazole coordinated gold(I) complexes (TA-Au) were revealed as the effective catalysts in promoting propargylic ester rearrangement and sequential allene hydration, giving the enones with excellent yields (up to 97% yields, 0.2% loading). The catalysts could also catalyze the more challenging Meyer-Schuster rearrangement (0.5% loading, up to 98% yields). The reported reaction confirmed TA-Au as a chemoselective catalyst in promoting alkyne activation with high efficiency and improved ligand economy. Copyright

[(NHC)AuI]-catalyzed formation of conjugated enones and enals: An experimental and computational study

The [(NHC)AuI]-catalyzed (NHC = N-heterocyclic carbene) formation of α,β-unsaturated carbonyl compounds (enones and enals) from propargylic acetates is described. The reactions occur at 60°C in 8 h in the presence of an equimolar mixture of [(NHC)AuCl] and AgSbF6 and produce conjugated enones and enals in high yields. Optimization studies revealed that the reaction is sensitive to the solvent, the NHC, and, to a lesser extent, to the silver salt employed, leading to the use of [(ItBu)AuCl]/ AgSbF6 in THF as an efficient catalytic system. This transformation proved to have a broad scope, enabling the stereoselective formation of (E)-enones and -enals with great structural diversity. The effect of substitution at the propargylic and acetylenic positions has been investigated, as well as the effect of aryl substitution on the formation of cinnamyl ketones. The presence or absence of water in the reaction mixture was found to be crucial. From the same phenylpropargyl acetates, anhydrous conditions led to the formation of indene compounds via a tandem [3,3] sigmatropic rearrangement/intramolecular hydroarylation process, whereas simply adding water to the reaction mixture produced enone derivatives cleanly. Several mechanistic hypotheses, including the hydrolysis of an allenol ester intermediate and SN2′ addition of water, were examined to gain an insight into this transformation. Mechanistic investigations and computational studies support [(NHC)AuOH], produced in situ from [(NHC)AuSbF6] and H 2O, instead of cationic [(NHC)AuSbF6] as the catalytically active species. Based on DFT calculations performed at the B3LYP level of theory, a full catalytic cycle featuring an unprecedented transfer of the OH moiety bound to the gold center to the C≡C bond leading to the formation of a gold-allenolate is proposed.