67173-95-9

Upstream product

• 292638-85-8 acrylic acid methyl ester 
• 93-55-0 1-phenyl-propan-1-one 
• 67-56-1 methanol 
• 80706-71-4 benzoyl-2 methyl-2 cyclobutanone 
• 673-32-5 1-Phenylprop-1-yne 
• 82215-67-6 1-Phenyl-1-(tri-n-butylstannyloxy)-propen 

Downstream Products

• 67173-96-0 cis-tetrahydro-5,6-dimethyl-6-phenyl-2H-pyran-2-one 
• 67173-96-0 trans-tetrahydro-5,6-dimethyl-6-phenyl-2H-pyran-2-one 
• 1433223-39-2 methyl 4-methyl-5-phenylhex-5-enoate 
• 1433223-32-5 4-methyl-5-phenylhex-5-enoic acid 
• 51975-22-5 5-methyl-6-phenyl-3,4-dihydro-2H-pyran-2-one 
• 230285-31-1 2-methyl-1-phenyl-1-(diphenylphosphatoxy)-5-(N-phthalimidoxy)pentane 
• 230285-30-0 2-methyl-1-phenyl-1-(diethylphosphatoxy)-5-(N-phthalimidoxy)pentane 
• 230285-29-7 1-(acetoxy)-2-methyl-1-phenyl-5-(N-phthalimidoxy)pentane 
• 230285-28-6 2-methyl-1-phenyl-5-(N-phthalimidoxy)-1-pentanol 
• 21464-01-7 2-benzyl-2-methyltetrahydrofuran 
• 230285-25-3 5-(tert-butyldiphenylsiloxy)-2-methyl-1-phenyl-1-(2-tetrahydropyranyloxy)pentane 
• 230285-27-5 2-methyl-1-phenyl-1-(2-tetrahydropyranyloxy)-5-(N-phthalimidoxy)pentane 
• 230285-24-2 5-(tert-butyldiphenylsiloxy)-2-methyl-1-phenyl-1-pentanol 
• 230285-26-4 2-methyl-1-phenyl-1-(2-tetrahydropyranyloxy)-5-pentanol 

Relevant academic research and scientific papers

Iodine(III)-Mediated Contraction of 3,4-Dihydropyranones: Access to Polysubstituted γ-Butyrolactones

Functionalized γ-butyrolactones are privileged structures in the field of medicinal chemistry; they are found in numerous natural products and synthetic compounds with diverse biological activities. The oxidative ring contraction of 3,4-dihydropyran-2-one derivatives represents a promising yet underappreciated strategy to access these compounds. To the best of our knowledge, very few examples of this strategy have been reported, with limited investigation of the influence of stereogenic centers on the starting dihydropyranones. We investigated the iodine(III)-mediated contraction of a representative set of dihydropyranone derivatives. The method gives rapid access to functionalized γ-butyrolactones in good yields. The reaction scope was investigated, and the method was found to support various levels of substituents, even enabling access to sterically congested quaternary centers. The stereoselectivity was investigated using chiral substrates and a chiral iodine(III) reagent.

Lewis Acid-Catalyzed Selective [2 + 2]-Cycloaddition and Dearomatizing Cascade Reaction of Aryl Alkynes with Acrylates

Combined Lewis acid, consisting of two or more Lewis acids, sometimes shows unique catalytic ability, and it may promote reactions which could not be catalyzed by any of the Lewis acids solely. On the other hand, the development of efficient methods for t

Michael addition of ketone enolates to α,β-unsaturated esters or amides in a one-pot procedure: Highly efficient effect of lithium salt generated in situ on organotin enolate

Michael addition of a metal ketone enolate to an α,β-unsaturated ester is thermodynamically disfavored, and thus, isolated metal enolates with an equimolar amount of Lewis acids or additives are usually required. This work describes the methodology of one

Michael addition of stannyl ketone enolate to α,β-unsaturated esters catalyzed by tetrabutylammonium bromide and an ab initio theoretical study of the reaction course

Michael addition of stannyl ketone enolates to α,β-unsaturated esters was accomplished in the presence of a catalytic amount of tetrabutylammonium bromide (Bu4NBr). Other typical systems using lithium enolate or silyl enolate with catalysts (TiCl4 or Bu4NF) failed to give the desired products. The bromide anion from Bu4NBr coordinates to the tin center in enolate to accelerate the conjugate addition where a five-coordinated tin species was generated. The coordination of the bromide anion significantly raises the HOMO level of tin enolate and enhances its nucleophilicity. The conjugate addition provides the intermediate Michael adduct, which has an ester enolate moiety, and the adduct immediately transforms to α-stannyl γ-ketoester by keto - enol tautomerization. This step contributes to the stabilization of the product system and leads to a thermodynamically favorable reaction course. An ab initio calculation reveals that the activation energy in the reaction using the bromide anion is lower than that of the reaction without using it. The transition state in either reaction course has a linear structure, not a cyclic one. This system can be applied to a variety of tin enolates and α,β-unsaturated carbonyls involving enoates, enones, and unsaturated amides.

Synthesis of tetrahydrofurans by a tandem hydrogen atom abstraction/ radical nucleophilic displacement sequence

(equation presented) The reaction of a series of 5-(N-phthalimidoxy)-1-phenyl-1-(diphenylphosphatoxy)pentanes with triphenyltin hydride and AIBN provides alkoxy radicals which undergo 1,5-hydrogen atom abstraction to give β-(phosphatoxy)alkyl radicals. These radicals then take part in a radical nucleophilic displacement leading, after chain transfer, to tetrahydrofurans.

Synthesis and reactions of [(((η6)-2-acylaryl)-C,O) tetracarbonylmanganese]-tricarbonylchromium complexes: Enhancement of diastereoselection during cyclopentaannulation

Cyclomanganation reactions of [(η6)-acylaryl]tricarbonylchromium complexes have been investigated. Three novel heterobimetallic complexes have been synthesised in moderate to good yield, with one being characterised by X-ray crystallography. Several modes of activating these bimetallic complexes towards coupling reactions with substituted alkenes and alkynes were investigated, including oxidative decarbonylation at room temperature, and thermal promotion. The stereochemistry of one of the cyclopentaannulated adducts has been established by X-ray crystallography. Thermal displacement of one of the CO ligands of the bimetallic complex 27 in the presence of PPh3 afforded a single adduct, the structure of which was established by X-ray crystallography. The chemistry of this novel bimetallic system was investigated.

ETUDE DES PETITS CYCLES-XLIV. UNE VOIE DE SYNTHESE DES ACYL-2 CYCLOBUTANONES

Organic peracid oxidation of α-cyclopropylidene ketones and acetals substituted in the vinylic position leads to the corresponding oxaspiropentyl ketones and acetals.Esters are also formed from the products of the Baeyer-Villiger oxidation; they are easily removed from the crude product.Unsubstituted oxaspiropentyl ketones are not obtained by this method; they are obtained by oxidation of oxaspiropentyl alcohols ( formed by epoxidation of α-cyclopropylidene alcohols).The isomerisation, either spontaneous or through reaction with lithium halides, of oxaspiropentyl ketones and acetals, gives 2-acyl-cyclobutanones and corresponding mono-acetals.These new unstable 1,3-diones must be stored in CCl4 solution.They are present in the dione form only.They add water and methanol, in acidic and even in neutral medium, leading to ring opening products. 2-Benzoyl cyclobutanone 4g is easily rearranged into 3,4-dihydro-6-phenyl 2-pyrone 12.Deacetalization of the 2-acyl-cyclobutanones mono-acetals 7B-11b into the corresponding diones is not possible even by the moist silicagel technique.

δ-LACTONES FROM GRIGNARD REACTIONS; THEIR ISOLATION AND STRUCTURE CHARACTERIZATION

Grignard reactions on methyl 4-methyl,5-oxo,5-phenyl (pX substituted) pentanoates 1-6 (X=H, Me, F, Cl, Br, OMe) produced mixtures of cis-(7-11) and trans-(12-16) tetrahydro 5,6-dimethyl-6-phenyl-2H-pyran-2-ones.They were isolated by HPLC and characterized

2-ACYLCYCLOBUTANONES FROM α-CYCLOPROPYLIDENE KETONES

Oxaspiropentyl ketones and acetals prepared from α-cyclopropylidene ketones and acetals undergo, with lithium halides, isomerisation to 2-acylcyclobutanones and monoacetals.