54709-18-1

Upstream product

• 563-80-4 3-methyl-butan-2-one 
• 3923-52-2 1,1-diphenyl-2-propyn-1-ol 
• 119-61-9 benzophenone 
• 908093-98-1 diazodiphenylmethane 
• 78-79-5 isoprene 
• 1210-39-5 3,3-diphenyl-2-propenal 
• 24470-78-8 isopropyltriphenylphosphonium iodide 
• 870-63-3 prenyl bromide 
• 58335-10-7 3-Methyl-2-butenylzinc bromide 
• 530-48-3 1,1-Diphenylethylene 
• 513-42-8 3-hydroxy-2-methyl-1-propene 
• 54709-17-0 3-(2,2-Diphenylcyclopropyl)-3-methyl-1,1-diphenyl-1-buten 

Relevant academic research and scientific papers

Contra-Thermodynamic Positional Isomerization of Olefins

A light-driven method for the contra-thermodynamic positional isomerization of olefins is described. In this work, stepwise PCET activation of a more substituted and more thermodynamically stable olefin substrate is mediated by an excited-state oxidant an

Neodymium-Promoted Highly Selective Carbon-Carbon Double Bond Formation of Ketones with Allyl Halides in the Presence of Diethyl Phosphite

The carbon-carbon double bond formation via neodymium-mediated Barbier-type reaction of ketones and allyl halides in the presence of diethyl phosphite is reported for the first time. The reaction is highly α-regioselective and was conveniently carried out under mild conditions in a one-pot fashion. From a synthetic point of view, a series of conjugated alkenes were obtained in moderate to good yields in this one-pot reaction with feasible reaction conditions.

1, 3-conjugated diene compound and preparation method and application thereof

The invention discloses a 1, 3-conjugated diene compound and a preparation method and application thereof. The invention provides a preparation method of the 1, 3-conjugated diene compound. The preparation method comprises the following steps: in an organic solvent and in the presence of a palladium catalyst, a phosphine ligand and an alkaline reagent, carrying out 1, 4-Pd migration/suzuki coupling reaction on an aromatic halide containing structural fragment shown in formula I and an alkenyl boron compound containing the structural fragment shown in formula II to obtain the compound containing a structural fragment of the 1, 3-conjugated diene shown in formula III. The preparation method has higher stereoselectivity and product configuration uniformity; a substrate has good universality,and is compatible with electron-deficient olefins, electron-rich olefins and polysubstituted olefins; and the method has the characteristics of mild reaction conditions, wide functional group compatibility and the like. The 1, 3-butadiene compound provided by the invention has high aggregation induced luminescence effect.

An Example of Ketone Olefination via Praseodymium-Mediated Barbier Reaction in the Presence of Diethyl Phosphite

The first example of carbon double-bond formation via praseodymium-mediated Barbier type reaction of ketones and allyl halides in the presence of diethyl phosphite is reported. The reaction is highly α-regioselective and conveniently carried out under mild conditions in a one-pot fashion. From a synthetic point of view, a series of conjugated alkenes were obtained in moderate to good yields in this one-pot reaction with practical reaction conditions.

Pd(0)-catalyzed cross-coupling of allyl halides with α-diazocarbonyl compounds or N-mesylhydrazones: Synthesis of 1,3-diene compounds

With palladium catalysis, allyl bromides or chlorides react with α-diazocarbonyl compounds or N-mesylhydrazones to afford 1,3-diene derivatives. The reaction represents a novel and efficient method for the synthesis of 1,3-butadiene derivatives. Mechanist

A novel ketone olefination via organozinc reagents in the presence of diphenyl phosphite

Carbonyl compounds react with organozinc reagents in the presence of diphenyl phosphite to give the corresponding olefins. A variety of 1,3-dienes and unsaturated esters were obtained in moderate to excellent yields under mild conditions. The Royal Society of Chemistry 2012.

In(OTf)3-catalyzed highly chemo- and regioselective head-to-tail heterodimerization of vinylarenes with 1,1-diarylethenes

Cross combination: The olefinic C-H bond in 1,1-diarylethenes selectively adds to the C=C double bond of substituted styrenes in a head-to-tail fashion under In(OTf)3 (OTf=triflate) catalysis (see scheme) while homo- and cyclodimerization reactions are suppressed. The high chemo- and regioselectivity of this intermolecular hydroalkenylation originates from the high stability and steric bulk of the diaryl-substituted tertiary carbocation intermediate. Copyright

Diazodiphenylmethane and monosubstituted butadienes: Kinetics and a new chapter of vinylcyclopropane chemistry

Diazodiphenylmethane (DDM) undergoes cycloadditions to 1-substituted buta-1,3-dienes exclusively at the C(3)=C(4) bond. At room temperature, the N2 loss from the initially formed 4,5-dihydro-3H-pyrazoles 2 is faster than the cycloaddition and furnishes the vinylcyclopropane derivatives 7 and 9 with structural retention at the C(1)=C(2) bond. 2-Substituted butadienes react with DDM at the C(3)=C(4) bond to give 12; isoprene, however, affords 3,4/1,2 products in the ratio of 86:14. DDM is a nucleophilic 1,3-dipole: 1-Cyanobutadiene reacts 400 times faster than 1-methoxybuta-1,3-diene (DMF, 40°). The log k2 for the additions to six 1-substituted butadienes show a linear correlation with σp (Hammett) and ρ = +2.9; the log k2 of five 2-substituted butadienes are linearly related to Taft's σI (ρ = +1.7). The structures of the vinylcyclopropanes 7, 9, and 12 are established by NMR spectra and oxidation. A cyclopropyl carbinyl cation is made responsible for the isomerization of 12, R = Ph, Me, by acetic acid to 4-substituted 1,1-diphenylpenta-1,3-dienes 25 and 29; TsOH at 200° converts 25 further to 9,10-dihydro-9-methyl-10-phenyl-9,10-ethanoanthracene (27). Thermal rearrangement of 7, 9, and 12 at 200-300° produces the 3- or 1-substituted 4,4-diphenylcyclopentenes 30 and 31. These give the same mass spectra as the vinylcyclopropanes, and an open-chain distonic radical cation is suggested as common intermediate. Besides spectroscopic evidence for the cyclopentene structures, hydrogenation and epoxidation are described; NMR data support the trans-attack by perbenzoic acid.

Efficient access to conjugated dienones and diene-diones from propargylic alcohols and enolizable ketones: A tandem isomerization/condensation process catalyzed by the sixteen-electron allyl-ruthenium(II) complex [Ru(η3-2-C3H4Me)(CO)(dppf)] [SbF 6]

A large variety of conjugated dienones R1R2C=CHCH= C(R3)C(=O)R4 and diene-diones R1R 2C=CHCH=C{C(=O)R3}C(=O)R4 have been synthesized in high yields by reacting terminal propargylic alcohols HO=CCR 1R2COH) with enolizable ketones R3CH 2C(=O)R4 and β-dicarbonyl compounds R 3C(=O)CH2C(=O)R4, respectively. The process, which is catalyzed by the 16e- (η3-allyl)- ruthenium(II) complex [Ru(η3-2-C3H4Me)(CO) (dppf)] [SbF6] associated with CF3CO2H, involves the initial isomerization of the propargylic alcohol into the corresponding α,β-unsaturated aldehyde R1R 2C=CHCHO (Meyer-Schuster rearrangement) and subsequent aldol-type condensation.

Trans-Selective Olefination of Carbonyl Compounds by Low-Valent Titanium-Mediated Dehydroxybenzotriazolylation

Lithiation with n-butyllithium of a variety of benzotriazole derivatives 1a-f and 5a-d, all containing a proton α to the benzotriazolyl moiety, gave anions which underwent addition to aliphatic, aromatic, and α,β-unsaturated aldehydes and cyclic and acyclic ketones. The resultant N-(β-hydroxyalkyl)benzotriazole derivatives 3a-m, 6a-g, 9a-d, and 10a were dehydroxybenzotriazolylated when treated with low-valent titanium to give alkenes 4a-m, dienes 7a- j, and triene 11a, with selectivity for the trans isomers without separation of diastereoisomeric intermediates. This method offers an alternative to the three most frequently used methods for the formation of alkenes from carbonyl compounds-the Wittig, Peterson, and Julia reactions-especially in the formation of tri- and tetrasubstituted alkenes.