17180-49-3

Upstream product

• 59967-14-5 4-iodo-1-pentene 
• 98-88-4 benzoyl chloride 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 106-95-6 allyl bromide 
• 146431-09-6 N,N-dimethylhydrazone de methyl-2 phenyl-1 pentene-4 one 
• 93-55-0 1-phenyl-propan-1-one 
• 71-43-2 benzene 
• 82215-67-6 1-Phenyl-1-(tri-n-butylstannyloxy)-propen 
• 2004-70-8 1-methylbuta-1,3-diene 
• 100-52-7 benzaldehyde 
• 557-40-4 Allyl ether 
• 107-18-6 allyl alcohol 
• 66323-99-7 trimethyl[(Z)-(1-phenyl-1-propenyl)oxy]silane 
• 762-72-1 allyl-trimethyl-silane 

Downstream Products

• 94922-10-8 2-bromo-4-benzoyl-4-methylhepta-1,6-diene 
• 78167-61-0 (2-methylpent-4-en-1-yl)benzene 
• 224426-62-4 1-phenyl-2-methyl-4,5-epoxypentan-1-one 
• 120536-73-4 (E)-2-methyl-1-phenylpent-3-en-1-one 
• 124306-44-1 (E)-2-methyl-1-phenyl-2-penten-1-one 
• 31366-05-9 (±)2-methyl-1-phenylpentan-1-one 
• 1616560-16-7 (E)-1-(2-methyl-1-phenylpent-4-en-1-ylidene)-2-phenylhydrazine 
• 94922-24-4 (3aS,6S,8aR)-6-Benzoyl-6-methyl-2-phenyl-4,5,6,7,8,8a-hexahydro-3aH-cyclopenta[f]isoindole-1,3-dione 
• 94922-14-2 1-benzoyl-1-methyl-5-methylenecyclohex-3-ene 
• 94922-13-1 1-benzoyl-1-methyl-3,4-bis(methylene)cyclopentane 
• 65912-65-4 3-Methyl-2-phenyl-1,5-hexadien 
• 145295-78-9 1-phenyl-2-methyl-2-(2-propen-1-yl)- 4-penten-1-one 

Relevant academic research and scientific papers

On the mechanism of the reaction of α-substituted ketones with allyltributylstannane

The mechanisms for the reaction of allyltributylstannane with a number of fragmentation probes, α-substituted acetophenones, were studied. All reactions were shown to proceed through free radical chain sequences since they could be initiated by AIBN and inhibited by m-dinitrobenzene (DNB). α-Halo- and α-(benzoyloxy)acetophenones (I and II, PhCOCR1R2X; X = F, Cl, Br, OCOPh; R1, R2 = H, Me) yielded the allylation products, PhCOCR1R2CH2CH=CH2), through a chain sequence involving as the propagation step: an electron transfer from Bu3Sn? to I and II, fragmentation of the ketyl anion PhCOCR1R2X?-, and addition of PhCOCR1R2? to allyltributylstannane. The reactions of α-(arylsulfonyl)acetophenones (IIIa-c, PhCOCR1R2Y, Y = SO2Tol-p), however, gave a nearly 1:1 mixture of allyl tosyl sulfone and the corresponding ketone, PhCOCHR1R2. The 1H and 13C NMR of the reaction mixture between allyltributylstannane and α-(p-methylbenzenesulfonyl)-isobutyrophenone substantiated the intermediacy of the tin enolate PhC(OSnBu3)=CMe2. These results suggested that a radical addition elimination mechanism was involved in the reactions of IIIa-c with allylstannane. The reaction of α-phenylthioacetophenone (IV, PhCOCH2SPh) gave both the electron transfer and the addition elimination products (PhCOCH2CH2CH=CH2, Ph-COCH3), indicating that both pathways were involved in the formation of the products.

α- And β-Functionalized Ketones from 1,3-Dienes and Aldehydes: Control of Regio- And Enantioselectivity in Hydroacylation of 1,3-Dienes

Ketones are among the most widely used intermediates in organic synthesis, and their synthesis from inexpensive feedstocks could be quite impactful. Regio- and enantioselective hydroacylation reactions of dienes provide facile entry into useful ketone-bearing chiral motifs with an additional latent functionality (alkene) suitable for further elaboration. Three classes of dienes, 2- or 4-monosubstituted and 2,4-disubstituted 1,3-dienes, undergo cobalt(I)-catalyzed regio- and enantioselective hydroacylation, giving products with high enantiomeric ratios (er). These reactions are highly dependent on the ligands, and we have identified the most useful ligands and reaction conditions for each class of dienes. 2-Substituted and 2,4-disubstituted dienes predominantly undergo 1,2-addition, whereas 4-substituted terminal dienes give highly enantioselective 4,1- or 4,3-hydroacylation depending on the aldehyde, aliphatic aldehydes giving 4,1-addition and aromatic aldehydes giving 4,3-addition. Included among the substrates are feedstock dienes, isoprene (US$1.4/kg) and myrcene (US$129/kg), and several common aldehydes. We propose an oxidative dimerization mechanism that involves a Co(I)/Co(III) redox cycle that appears to be initiated by a cationic Co(I) intermediate. Studies of reactions using isolated neutral and cationic Co(I) complexes confirm the critical role of the cationic intermediates in these reactions. Enantioselective 1,2-hydroacylation of 2-trimethylsiloxy-1,3-diene reveals a hitherto undisclosed route to chiral siloxy-protected aldols. Finally, facile syntheses of the anti-inflammatory drug (S)-Flobufen (2 steps, 92% yield, >99:1 er) and the food additive (S)-Dihydrotagetone (1 step, 83% yield; 96:4 er) from isoprene illustrate the power of this method for the preparation of commercially relevant compounds.

The salt-free nickel-catalysed α-allylation reaction of ketones with allyl alcohol and diallylether

The nickel-catalysed α-allylation of ketones with allyl alcohol and diallylether has been performed under neutral conditions. As no base is involved, the products are synthesized without salts as side products. The dppf/Ni(cod)2 catalytic system in MeOH at 80 °C has been shown as the most effective reaction system to afford tetrasubstituted derivatives from various cyclic and acyclic ketones with one or two mobile protons. This process combined with a metathesis step yields spirocyclic compounds according to a salt free synthetic sequence.

Enolonium Species—Umpoled Enolates

Enolonium species/iodo(III)enolates of carbonyl compounds have been suggested to be intermediates in a wide variety of hypervalent iodine induced chemical transformations of ketones, including α-C?O, α-C?N, α-C?C, and α-carbon–halide bond formation, but they have never been characterized. We report that these elusive umpoled enolates may be made as discrete species that are stable for several minutes at ?78 °C, and report the first spectroscopic identification of such species. It is shown that enolonium species are direct intermediates in C?O, C?N, C?Cl, and C?C bond forming reactions. Our results open up chemical space for designing a variety of new transformations. We showcase the ability of enolonium species to react with prenyl, crotyl, cinnamyl, and allyl silanes with absolute regioselectivity in up to 92 % yield.

Base-mediated cascade rearrangements of aryl-substituted diallyl ethers

Two base-mediated cascade rearrangement reactions of diallyl ethers were developed leading to selective [2,3]-Wittig-oxy-Cope and isomerization-Claisen rearrangements. Both diaryl and arylsilyl-substituted 1,3-substituted propenyl substrates were examined, and each exhibits unique reactivity and different reaction pathways. Detailed mechanistic and computational analysis was conducted, which demonstrated that the role of the base and solvent was key to the reactivity and selectivity observed. Crossover experiments also suggest that these reactions proceed with a certain degree of dissociation, and the mechanistic pathway is highly complex with multiple competing routes.

Copper-catalyzed cyclization and azidation of γ,δ-unsaturated ketone O-benzoyl oximes

An intramolecular imination/azidation sequence has been realized through the tetrakis(acetonitrile)copper(I) hexafluorophophate [Cu(CH3CN)4PF6]-catalyzed reaction of γ,δ-unsaturated ketone O-benzoyl oximes with trimethylsi

Investigation of a novel diamine based chiral auxiliary in the asymmetric alkylation of ketones

A novel chiral auxiliary containing a pyrrolidine ring has been utilised in the preparation of various chiral ketones with good to excellent enantioselectivities (up to 92%). It has been successfully employed in aldol and Michael reactions giving moderate to high selectivity.

Cross-coupling reaction of α-chloroketones and organotin enolates catalyzed by zinc halides for synthesis of γ-diketones

The reaction of tin enolates 1 with α-chloro- or bromoketones 2 gave γ-diketones (1,4-diketones) 3 catalyzed by zinc halides. In contrast to the exclusive formation of 1,4-diketones 3 under catalytic conditions, uncatalyzed reaction of 1 with 2 gave aldol-type products 4 through carbonyl attack. NMR study indicates that the catalyzed reaction includes precondensation between tin enolates and α-haloketones providing an aldol-type species and their rearrangement of the oxoalkyl group with leaving halogen to produce 1,4-diketones. The catalyst, zinc halides, plays an important role in each step. The carbonyl attack for precondensation is accelerated by the catalyst as Lewis acid and the intermediate zincate promotes the rearrangement by releasing oxygen and bonding with halogen. Various types of tin enolates and α-chloro and bromoketones were applied to the zinc-catalyzed cross-coupling. On the other hand, the allylic halides, which have no carbonyl moiety, were inert to the zinc-catalyzed coupling with tin enolates. The copper halides showed high catalytic activity for the coupling between tin enolates 1 and organic halides 7 to give γ,δ-unsaturated ketones 8 and/or 9. The reaction with even chlorides proceeded effectively by the catalytic system.

Rhodium promoted isomerisation of allylic alkoxides: A new method for enolate anion formation

Transition metal mediated isomerisation of allylic alkoxides is presented as a new method for enolate anion generation. The scope and limitations of enolate formation with the catalysts [Rh(dppe)(THF)2]+ClO4- and (Ph3P)3RhCl are explored and the synthetic potential of the methodology demonstrated in the stereoselective formation and reactions of certain ketone and aldehyde enolates.

Regio- and stereoselectivity in the cyclization of enolates derived from 4,5-, 5,6-, and 6,7-epoxy-1-phenyl-1-alkanones. Competition between C- and O- alkylation

The results obtained in the base-catalyzed intramolecular cyclization of enolates derived from some representative 4,5-, 5-6, and 6,7-epoxy ketones and of the corresponding alkenes are discussed. The LHMDS/Sc(OTf)3 protocol on epoxy ketones app