65495-77-4

Upstream product

• 131190-16-4 (E)-4-Ethoxy-2-methyl-1-phenyl-but-3-en-1-one 
• 85684-59-9 percarbonate de O,O-t-butyle et O-vinyle 
• 93-55-0 1-phenyl-propan-1-one 
• 1450-07-3 1-benzoylethylidenetriphenylphosphorane 
• 2114-00-3 2-bromo-1-phenyl-1-propanone 
• 109-92-2 ethyl vinyl ether 
• 1074-12-0 phenylglyoxal hydrate 
• 123-73-9 trans-Crotonaldehyde 
• 611-73-4 Benzoylformic acid 
• 123-73-9 crotonaldehyde 
• 85370-89-4 α-ethoxycrotyltributyltin 
• 98-88-4 benzoyl chloride 

Relevant academic research and scientific papers

Visible-Light Photocatalytic Preparation of 1,4-Ketoaldehydes and 1,4-Diketones from α-Bromoketones and Alkyl Enol Ethers

A Ru2+-photocatalyzed, visible-light-mediated ATRA reaction for the straightforward preparation of 1,4-ketoaldehydes, 1,4-diketones, and 1,4-ketoesters, which are of difficult access by other means, is reported herein. This method employs readily accessible α-bromoketones and alkyl vinyl ethers as starting materials, allowing the construction of secondary, tertiary, and challenging quaternary centers. In addition, the synthetic usefulness of this method is illustrated by applying it to the construction of substituted pyrroles.

Stereocontrolled Synthesis of 1,4-Dicarbonyl Compounds by Photochemical Organocatalytic Acyl Radical Addition to Enals

We report a visible-light-mediated organocatalytic strategy for the enantioselective acyl radical conjugate addition to enals, leading to valuable 1,4-dicarbonyl compounds. The process capitalizes upon the excited-state reactivity of 4-acyl-1,4-dihydropyridines that, upon visible-light absorption, can trigger the generation of acyl radicals. By means of a chiral amine catalyst, iminium ion activation of enals ensures a stereoselective radical trap. We also demonstrate how the combination of this acylation process with a second catalyst-controlled bond-forming event allows to selectively access the full matrix of all possible stereoisomers of the resulting 2,3-substituted 1,4-dicarbonyl products.

Bioinspired Radical Stetter Reaction: Radical Umpolung Enabled by Ion-Pair Photocatalysis

A bioinspired, intermolecular radical Stetter reaction of α-keto acids and aldehydes is disclosed that is contingent on a formal “radical umpolung” concept. Enabled by secondary amine activation, electrostatic recognition ensures that the α-ketocarboxylic acids, which function as latent acyl radicals, are proximal to the in situ generated iminium salts. This photoactive contact ion pair is an electron donor–acceptor (EDA) complex, and undergoes facile single electron transfer (SET) and rapid decarboxylation prior to radical–radical recombination. Importantly, decarbonylation is mitigated by this strategy. The initial computational validation on which the process is predicated matches closely with experiment. Synergising organo- and photocatalysis activation principles finally expands the mechanistic and synthetic scope of the classic Stetter reaction to include α,β-unsaturated aldehydes as acceptors.

Organocatalytic Redox Isomerization of Electron-Deficient Allylic Alcohols: Synthesis of 1,4-Ketoaldehydes

An organocatalytic redox isomerization strategy has been developed for the synthesis of 1,4-ketoaldehydes. DABCO was found to be the best catalyst for the isomerization of -hydroxy enones. With 20 mol % of DABCO as catalyst and DMSO as the solvent high yi

ORGANOTIN HOMOENOLATE EQUIVALENTS - ACCESS TO β-ACYL- AND β-ARYL-PROPIONALDEHYDES THROUGH HETEROSUBSTITUTED ALLYLTINS AND VINYLTINS

Although, α-ethoxycrotyltributyltin can be used as an equivalent of the homoenolate anion CH3-CHCH2CHO in reactions with acyl chlorides, the non-substituted α-ethoxyallyltributyltin could not be employed in this way. γ-Methoxyvinyltins, easily prepared by hydrostannation of propargylic ethers, are successfully employed as synthetic equivalents of the homoenolate anions -CH2CH2CHO and -CH2CH2COCH3 in reactions with acyl chlorides.A silylated γ-methoxyvinyltin, which is both a vinyltin and an allylsilane, reacts with acyl chlorides and aryl bromides as a promising equivalent of the homoenolate anion -CH2CH2CHO and tolerates a wide range of other reactive functional groups.

SELECTIVITY IN REACTIONS INVOLVING α-ALKOXYALLYLTRIBUTYLTINS

The behaviour of α-alkoxyallyltributyltins has been studied in terms of chemo-, regio- and stereoselectivity.Chemoselectivity is readily controlled by the experimental conditions, as exemplified by the reaction of p-bromobenzaldehyde with α-ethoxycrotyltr

Obtention d'aldehydes γ-fonctionnels au cours de la thermolyse du percarbonate de O,O-t-butyle et O-vinyle en solution

Owing to its peroxyester group, O,O-tert-butyl and O-vinyle peroxycarbonate may act as a free radical initiator in solution, but also, due to the presence of the vinylic insaturation, as a substrate for free radical addition reactions. - In such solvents as cumene which give free radicals unable to add to the double bond, the peroxycarbonate merely behaves as a vinyloxy radicals generator.It is thus possible to observe these radicals reacting either as formylmethyl radicals or as acetyl radicals. - In solvents such as cyclohexane which give free radicals able to add to the double bond, the reaction results in the substitution of formylmethyl groups to labile hydrogens of the solvent. - By applying the reaction to such compounds as ketones, ethers, acids and their derivatives, we could obtain γ-functional aldehydes (γ-ketoaldehydes, γ-oxaaldehydes and derivatives of succinaldehydic acids).These products are often difficult to prepare by other routes and until now only some of them have been described.