76118-17-7

Upstream product

• 17851-98-8 1-phenyl-1-(tributylstannyloxy)ethene 
• 503-60-6 3,3-dimethyl-allyl chloride 
• 870-63-3 prenyl bromide 
• 107-86-8 3,3-dimethyl acrylaldehyde 
• 108-86-1 bromobenzene 
• 95465-44-4 3-methyl-1-phenylbut-2-en-1-ol 
• 5650-07-7 3-methyl-1-phenyl-but-2-en-1-one 
• 1826-67-1 vinyl magnesium bromide 
• 100-59-4 phenylmagnesium chloride 
• 3350-78-5 3,3-Dimethylacryloyl chloride 
• 13735-81-4 1-styrenyloxytrimethylsilane 
• 18293-99-7 Prenyltrimethylsilane 
• 598-25-4 Dimethylallene 
• 614-20-0 3-oxo-3-phenylpropionic acid 

Relevant academic research and scientific papers

Visible Light Mediated Photocatalytic N-Radical Cascade Reactivity of O,δ-Unsaturated N-Arylsulfonylhydrazones: A General Approach to Structurally Diverse Tetrahydropyridazines

Tetrahydropyridazines are of particular interest for their versatility as intermediates in organic synthesis and display pharmacological activity in several domains. Here, we describe the photocatalytic synthesis of different tetrahydropyridazines starting from O,δ-unsaturated N-arylsulfonylhydrazones. Simple structural changes of substrates result into three different pathways beginning from a common N-hydrazonyl radical, which evolves through a domino carboamination/dearomatization, a HAT process, or a photoinduced radical Smiles rearrangement to afford diverse tetrahydropyridazines. All reactions are carried out in very mild conditions, and the quite inexpensive [Ru(bpy)3]Cl2 is used as the catalyst. Preliminary mechanism studies are presented, among them luminescence and electrochemical characterization of the involved species. Computational studies allow to rationalize the mechanism in accord with the experimental findings.

Palladium-Catalyzed Hydrocarbonylative Cyclization of 1,5-Dienes

A novel and atom-economic palladium-catalyzed isomerization-hydrocarbonylative cyclization reaction of 1,5-dienes to 2-alkylidenecyclopentanones has been developed, which provides a rapid and straightforward approach to 2-alkylidenecyclopentanones with high stereoselectivity. The reaction was found to proceed via alkene isomerization and selective hydrocarbonylative cyclization to generate 2-alkylidenecyclopentanones with high selectivity.

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.

Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to allenes: Efficient construction of tertiary and quaternary carbon centers

A rhodium-catalyzed chemo- and regioselective intermolecular decarboxylative addition of β-ketoacids to terminal allenes is reported. Using a Rh(I)/DPPF system, tertiary and quaternary carbon centers were formed with exclusively branched selectivity under mild conditions. Preliminary mechanism studies support that the carbon-carbon bond formation precedes the decarboxylation and the reaction occurs in an outer-sphere mechanism.

Highly regioselective [3,3] rearrangement of aliphatic allyl vinyl ethers catalyzed by a metalloporphyrin complex, Cr(TPP)Cl

The Claisen rearrangement of simple aliphatic allyl vinyl ethers catalyzed by a metalloporphyrin, Cr(TPP)Cl, is described. The porphyrin-based Lewis acid catalyst can effectively accelerate the rearrangement via a concerted [3,3] pathway with a minimal degree of bond ionization of the substrates, providing the corresponding Claisen products in moderate to high yields and almost perfect regioselectivity at low catalyst loading.

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.

The Oxidative Coupling Reaction of Allylstannanes with Trimethylsilyl Enol Ethers

γ,δ-Unsaturated ketones were obtained by the reaction of trimethylsilyl enol ethers with allylstannanes in the presence of tin(IV) or copper(II) salt in good yields.

Base Catalysed Rearrangements involving Ylide Intermediates. Part 2. The Stevens and Sigmatropyc Rearrangements of Allylic Ammonium Ylides

The base catalysed rearrangements of the quaternary ammonium salts (9) usually gives the sigmatropic rearrangement product (10) rather than the Stevens rearrangement product (11).An earlier claim has been corrected: the corresponding reaction