70624-80-5

Upstream product

• 100-52-7 benzaldehyde 
• 51849-03-7 Adamantan-1-ylmethylene-triphenyl-λ⁵-phosphane 
• 100-42-5 styrene 
• 768-90-1 1-Adamantyl bromide 
• 768-93-4 1-iodoadamantane 
• 18723-83-6 trans-(2-(ethylsulfonyl)vinyl)benzene 
• 536-74-3 phenylacetylene 
• 281-23-2 adamantane 
• 621-82-9 Cinnamic acid 
• 5418-11-1 phenyl styryl sulfone 
• 21245-43-2 tert-butyl (3r,5r,7r)-adamantane-1-carboperoxoate 
• 828-51-3 1-Adamantanecarboxylic acid 
• 118334-83-1 1,3-dioxoisoindolin-2-yl (3r,5r,7r)-adamantane-1- carboxylate 
• 16212-06-9 phenyl styryl sulfone 

Relevant academic research and scientific papers

Peroxide promoted tunable decarboxylative alkylation of cinnamic acids to form alkenes or ketones under metal-free conditions

A tunable decarboxylative alkylation of cinnamic acids with alkanes was developed to form alkenes or ketones under transition metal-free conditions. In the presence of DTBP or DTBP/TBHP, the reaction gave alkenes and ketones respectively via a radical mechanism in moderate to good yields. This journal is

Vinyl Sulfonium Salts as the Radical Acceptor for Metal-Free Decarboxylative Alkenylation

Vinyl sulfonium salts typically act as an electrophilic Michael acceptor, thus initiating many tandem cyclization reactions. Herein, we disclosed the novel reactivity of vinyl sulfonium salts as a radical acceptor. Using redox-active ester as an alkyl rad

Photo-induced Decarboxylative Heck-Type Coupling of Unactivated Aliphatic Acids and Terminal Alkenes in the Absence of Sacrificial Hydrogen Acceptors

1,2-Disubstituted alkenes such as vinyl arenes, vinyl silanes, and vinyl boronates are among the most versatile building blocks that can be found in every sector of chemical science. We herein report a noble-metal-free method of accessing such olefins through a photo-induced decarboxylative Heck-type coupling using alkyl carboxylic acids, one of the most ubiquitous building blocks, as the feedstocks. This transformation was achieved in the absence of external oxidants through the synergistic combination of an organo photo-redox catalyst and a cobaloxime catalyst, with H2 and CO2 as the only byproducts. Both control experiments and DFT calculations supported a radical-based mechanism, which eventually led to the development of a selective three-component coupling of aliphatic carboxylic acids, acrylates, and vinyl arenes. More than 90 olefins across a wide range of functionalities were effectively synthesized with this simple protocol.

Iron-Catalyzed Vinylic C?H Alkylation with Alkyl Peroxides

A variety of alkyl peresters and alkyl diacyl peroxides, which are readily accessible from carboxylic acids, are utilized as general primary, secondary, and tertiary alkylating reagents for iron-catalyzed vinylic C?H alkylation of vinyl arenes, dienes, and 1,3-enynes. This transformation affords olefinic products in up to 98 % yield with high E/Z values. A broad range of functionalities, including carboxyl, boronic acid, methoxy, ester, amino, and halides, are tolerated. This protocol provides a facile approach to some olefins that are difficult to access, and hence, offers an alternative to existing systems. The synthetic utility of this method is demonstrated by late-stage functionalization of selected natural-product derivatives.

Palladium/Light induced radical alkenylation and allylation of alkyl iodides using alkenyl and allylic sulfones

Alkenylation and allylation of alkyl iodides with alkenyl and allyl sulfones, respectively, took place under Pd/photoirradiation system. The initial alkyl radical, derived from a single electron transfer between Pd(0) and RI, underwent the title transformations. Pd(0) was regenerated through a reductive elimination of PhSO2PdI, which is formed by the combination of the sulfonyl radical and the palladium radical. The addition of water was effective, presumably by pushing the equilibrium through hydrolysis of PhSO2I.

Irradiation-Induced Palladium-Catalyzed Decarboxylative Heck Reaction of Aliphatic N-(Acyloxy)phthalimides at Room Temperature

It is reported that Pd(PPh3)2Cl2 in combination with 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) under irradiation of blue LEDs efficiently catalyzes a decarboxylative Heck reaction of vinyl arenes and vinyl heteroarenes with aliphatic N-(acyloxy)phthalimides at room temperature. A broad scope of secondary, tertiary, and quaternary carboxylates, including α-amino acid derived esters, can be applied as amenable substrates with high stereoselectivity. The experimental observation was explained by excitation-state reactivity of the palladium complex under irradiation to induce single-electron transfer to activate N-(acyloxy)phthalimides, and to suppress undesired β-hydride elimination of alkyl palladium intermediates.

Photoredox catalysis enabled alkylation of alkenyl carboxylic acids with: N -(acyloxy)phthalimide via dual decarboxylation

A ruthenium based photoredox catalyst in combination with a substoichiometric amount of 1,4-diazabicyclo[2.2.2]octane (DABCO) efficiently catalyzed dual decarboxylative couplings between alkenyl carboxylic acids and N-(acyloxy)phthalimides derived from aliphatic carboxylic acids, delivering alkylated styrene derivatives in a high regio- and stereo-selective manner under mild reaction conditions. Various types of secondary, tertiary, and quaternary aliphatic carboxylic acids as well as α-amino acids can be used as suitable substrates. Mechanistic analysis suggested that the reaction proceeds through a radical mechanism mediated by a Ru(i)/Ru(ii) catalytic cycle with DABCO acting both as the base and the co-catalyst for single electron transfer.

The aminocyclodextrin/Pd(OAc)2 complex as an efficient catalyst for the Mizoroki-Heck cross-coupling reaction

An aminocyclodextrin/Pd(OAc)2 complex is used as an efficient, reusable catalyst in the Mizoroki-Heck reaction of aryl halides/triflates with olefins to give carbon-carbon-coupled products in good to excellent yields. This simple, efficient catalytic system is applicable to a wide range of aryl and heteroaryl halides/triflates and olefins. This environmentally benign procedure is less hazardous, milder, uses a catalytic amount of ligand and Pd(OAc) 2, avoids an inert atmosphere, and catalyst recovery and reusability are achieved. Copyright

Allylsilanes in "tin-free" oximation, alkenylation, and allylation of alkyl halides

Tin-free oximation, vinylation, and allylation of alkyl halides have been developed by using allylsilanes as di-tin surrogates. Initiation of the radical process with a peroxide provides the silyl radical, which can abstract a halogen from the corresponding alkyl halide. The resulting carbon-centered radical then adds to various acceptors, including a sulfonyloxime, a vinylsulfone, and an allylsulfone, leading to formation of the desired products along with the corresponding allylsulfone resulting from the reaction of the PhSO2 radical with the allylsilane precursor. Better results were generally obtained with methallylsilane 1b than with 1a. This observation was rationalized by invoking the higher nucleophilicity of 1b and the faster β-fragmentation of the corresponding β-silyl radical intermediate. Calculation of the energy barrier for the β-fragmentation of a series of β-silyl radicals at the DFT level supported this hypothesis. Finally, a second version of these oximation and vinylation reactions, based on the utilization of 3-tris(trimethylsilyl)silylthiopropene, was devised, affording the desired oximes and olefins in reasonable yields. This strategy allowed the title reaction to be performed under milder conditions (AIBN, benzene, 80°C), as a result of the easier β-fragmentation of the C-S bond as compared with the C-Si bond.

Silver-catalyzed regioselective carbomagnesiation of alkynes with alkyl halides and Grignard reagents

A silver-catalyzed carbomagnesiation of alkynes with alkyl halides and Grignard reagents afforded alkenyl Grignard reagents regioselectively, where the alkyl group of the alkyl halide, but not that of the Grignard reagent, was introduced into the alkyne.