77915-31-2

Upstream product

• 33795-03-8 2,2-dimethyl-1,4,4-triphenylbut-3-en-1-one 
• 104581-48-8 2-methyl-4,4-diphenylbut-3-en-2-ol 
• 15295-29-1 4,4-diphenyl-4-hydroxybut-2-ene 
• 5820-02-0 2,2-dimethyl-4,4-diphenyl-but-3-enal 
• 3017-69-4 2-methyl-1-propenylbromide 
• 4545-20-4 benzophenone tosylhydrazone 
• 119-61-9 benzophenone 
• 1458-98-6 2-methyl-3-bromo-1-propene 
• 1244620-37-8 N'-(diphenylmethylene)methanesulfonohydrazide 
• 837-66-1 1,1-diphenyl-1 buten-3-one 
• 1210-39-5 3,3-diphenyl-2-propenal 
• 144758-68-9 3,3-dimethyl-5,5-diphenylpent-4-en-2-one O-trifluoroacetyloxime 
• 81112-28-9 methyl 2-methylprop-2-enyl carbonate 
• 525-06-4 diphenyl ketene 

Relevant academic research and scientific papers

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.

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

Synthesis of dienes by palladium-catalyzed couplings of tosylhydrazones with aryl and alkenyl halides

Two different combinations of coupling partners can be employed for the synthesis of conjugated dienes by palladium-catalyzed cross-coupling with tosylhydrazones: α,β-unsaturated ketone and aryl halide or alkenyl halide and non-conjugated tosylhydrazone. Depending on the substrate, a vinylogous hydride elimination is responsible for the formation of the final dienes. Copyright

SmI2-Mediated 3-exo-trig Cyclization of β,γ- unsaturated carbonyl compounds: Diastereoselective synthesis of cyclopropanols

SmI2-mediated 3-exo-trig cyclizations of β,γ- unsaturated carbonyl compounds to generate cyclopropanols are not generally observed processes. The reported examples are limited to β,γ- unsaturated carbonyl compounds that possess ester groups con

Chemically Efficient Aza-Di-?-Methane Photoreactivity with Novel Stable Derivatives of β,γ-Unsaturated Carbonyl Compounds

The syntheses of new stable derivatives of β,γ-unsaturated carbonyl compounds such as 2,2-dimethyl-4,4-diphenylbut-3-enal 6 and 3,3-dimethyl-5,5-diphenylpent-4-en-2-one 7 are described.The majority of these derivatives undergo efficient aza-di-?-methane r

Reactions of Some Cyclopropanes Activated by a Spiro-Linked Fluorene. Importance of Electronic Matching of a Reacting Partner in Thermal Cycloaddition with TCNE and Ring-Opening Dehydrogenation with DDQ

Cyclopropanes 1a-c substituted both by a fluorene group, linked in a spiro fashion, and by gem-dialkyl groups were found to be highly reactive in the reaction with a certain strongly electron-demanding unsaturated compound, such as TCNE and DDQ.Namely, 1 reacted with TCNE in the dark to give a 2 + ?2> type cycloadduct 5, whereas 1 was dehydrogenated by DDQ to afford 4 when one of the alkyl substituents is a methyl.The resulting 4 reacted with another molecule of DDQ to afford 10 ultimately.In contrast to 1, the corresponding diphenyl derivatives 2a-c were reluctant to undergo these reactions.Moreover, chloranil was unable to dehydrogenate spiro-activated 1 under similar conditions.It is thus concluded that the dark reaction occurs when the reagent and reactant match electronically in a donor-acceptor sense.Under the illumination of visible light, however, the same type of reactions was found to take place even with a mismatched pair.Namely, the reactions of 2a with TCNE, 2b or 2c with DDQ, and 1b, 1c, 2b, or 2c with chloranil were all brought about when the mixture was irradiated by a halogen lamp.In the chloranil dehydration, the expected diene remained intact in the product mixture.All these results suggest that the TCNE cycloaddition as well as the quinone dehydrogenation are initiated by a single-electron transfer (SET).The effect of alkyl substituents in 1 on the rate (reactivity sequence: 1a > 1b > 1c > 8) and the solvent polarity effect on the rate are indicative of the rate-controlling production of a radical ion pair, which would then react to give ultimate products.Possible routes for the observed products are proposed (Scheme I) and discussed.

Palladium-Complex-Catalyzed Reactions of Ketenes with Allylic Carbonates or Acetates. Novel Syntheses of α-Allylated Carboxylic Esters and 1,3-Dienes

Diphenylketene and ethylphenylketene react with allylic carbonates or acetates in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium to give α-allylated esters or 1,3-dienes, respectively.For example, the reaction of diphenylketene with allyl methyl carbonate in DMF at 0 deg C gave methyl 2,2-diphenyl-4-pentenoate in 67percent yield.The reaction of diphenylketene with allyl acetate in benzene at 25 deg C gave 1,1-diphenyl-1,3-butadiene in 72percent yield.Marked solvent effects were observed.

Palladium-catalysed Reactions of Ketenes with Allyl Acetates or Allyl Carbonates: Novel Syntheses of 1,3-Dienes and Allylated Esters

The reaction of arylketenes with allyl acetates or allyl carbonates catalysed by tetrakis(triphenylphosphine)palladium selectively gives 1,3-dienes or allylated esters, respectively, in high yields.

PHOTOCHEMISTRY OF β,γ-UNSATURATED KETONES - V ; THE DIRECT IRRADIATION OF SOME γ-PHENYL β;γ-ENONES

The photochemistry of some members of the two series of γ-phenyl substituted acyclic β,γ-unsaturated ketones 1 and 2 upon direct irradiation with λ 310 nm has been investigated, viz 1c-1h and 2b+2c.The alkyl substituted (E)-5-phenyl-4-penten-2-ones 1c-1h yield the corresponding 1,3-acyl shift products and (Z)-isomers, and 1g and 1h in addition two decarbonylated products. 2b only yields the (Z)-isomer and some benzaldehyde, but 2c yields the 1,3-acyl shift product, the ODPM product, three hydrocarbons formed by disproportionation of the allyl radical, and some benzaldehyde.The β-phenyl β,γ-UK 3a proved to be photostable.The 1,3-acyl shift products of 1c-1h result mainly from the singlet excited state in a cage radical process.The exclusive formation of the (E)-configuration of the 1,3-acyl shift product is explained in terms of conformational preference of the intermediate allyl radical.It is proposed that the formation of the (Z)-isomer proceeds from 1T(?-?*) which is populated according to .Evidence is presented which supports the proposed mechanism.The β,γ-UK 2b containing a benzoyl moiety leads to a higher degree of (E)-(Z) isomerization than the corresponding 1d which has an acetyl moiety.The triplet energies of (E)- and (Z)-1h are 56 and ca 70 kcal/mol respectively.