36144-55-5

Upstream product

• 1871-76-7 diphenylacetic acid chloride 
• 1439-36-7 1-triphenylphosphoranylidene-2-propanone 
• 82101-33-5 2,5-diphenyl-4-pentyn-2-ol 

Downstream Products

• 145207-61-0 2-(Diphenylmethylidene)-4-methylbut-3-en-4-olide 
• 109244-97-5 (Z)-5,5-Diphenyl-4-phenylamino-pent-3-en-2-one 
• 109244-96-4 5,5-Diphenyl-4-phenylsulfanyl-pent-4-en-2-one 

Relevant academic research and scientific papers

Novel preparation method of polysubstituted alpha-propadiene aldehyde and alpha-propadiene ketone compounds

The invention provides a novel method for synthesizing polysubstituted alpha-propadiene aldehyde and alpha-propadiene ketone compounds by using high acetylene alcohol as a raw material under the milder reaction conditions. The method uses the high acetylene alcohol as a substrate, and the polysubstituted propadiene aldehyde and propadiene ketone compounds are simply and directly synthesized by taking Slectfluor as an oxidizing agent and using acetonitrile as a solvent under the reaction condition that copper chloride is used as a catalyst and 1,2-bis (diphenylphosphine) is used as a ligand. According to the reaction, the high acetylene alcohol is used as a substrate for synthesizing the polysubstituted propadiene aldehyde and propadiene ketone compounds for the first time, the reaction conditions are milder, and fewer steps are needed by the reaction. Furthermore, the invention also has the characteristics of being simple in raw material preparation, safe to operate, high in yield, andthe like, thus having a great industrial application value.

Metal-catalyzed 1,2-shift of diverse migrating groups in allenyl systems as a new paradigm toward densely functionalized heterocycles

A general, mild, and efficient 1,2-migration/cycloisomerization methodology toward multisubstituted 3-thio-, seleno-, halo-, aryl-, and alkyl-furans and pyrroles, as well as fused heterocycles, valuable building blocks for synthetic chemistry, has been developed. Moreover, regiodivergent conditions have been identified for C-4 bromo- and thio-substituted allenones and alkynones for the assembly of regioisomeric 2-hetero substituted furans selectively. It was demonstrated that, depending on reaction conditions, ambident substrates can be selectively transformed into furan products, as well as undergo selective 6-exo-dig or Nazarov cyclizations. Our mechanistic investigations have revealed that the transformation proceeds via allenylcarbonyl or allenylimine intermediates followed by 1,2-group migration to the allenyl sp carbon during cycloisomerization. It was found that 1,2-migration of chalcogens and halogens predominantly proceeds via formation of irenium intermediates. Analogous intermediate can also be proposed for 1,2-aryl shift. Furthermore, it was shown that the cycloisomerization cascade can be catalyzed by Bransted acids, albeit less efficiently, and commonly observed reactivity of Lewis acid catalysts cannot be attributed to the eventual formation of proton. Undoubtedly, thermally induced or Lewis acid-catalyzed transformations proceed via intramolecular Michael addition or activation of the enone moiety pathways, whereas certain carbophilic metals trigger carbenoid/oxonium type pathway. However, a facile cycloisomerization in the presence of cationic complexes, as well as observed migratory aptitude in the cycloisomerization of unsymmetrically disubstituted aryl- and alkylallenes, strongly supports electrophilic nature for this transformation. Full mechanistic details, as well as the scope of this transformation, are discussed.

Metal-catalyzed [1,2]-alkyl shift in allenyl ketones: Synthesis of multisubstituted furans

(Chemical Equation Presented) Even fused furans can be prepared by cycloisomerization of substituted allenyl ketones. The cascade reaction involves a [1,2]-migration of alkyl or aryl groups in allenyl ketones as the key step. Facile reaction in the presence of cationic complexes, as well as migratory aptitude in the cycloisomerization of unsymmetrically substituted allenes, strongly supports an electrophilic mechanism for this transformation.

A convenient and practical route to novel α-allenic ketones through a Wittig reaction

A convenient synthesis of novel 5-arylpenta-3,4-diene-2-ones (3a-g) through a Wittig reaction of acetylmethylentriphenylphosphorane (2) with arylketenes is described.

Enolates of α-allenyl ketones: Formation and aldol reactions of cumulenolates

Enolization of α-allenyl ketones under kinetic conditions, followed by reactions with aldehydes and ketones, affords aldol products that suggest the intermediacy of cumulenolates, formed via the abstraction of a vinylic α-hydrogen. The origin for this marked difference with α-alkenyl ketones is attributed to the enhanced acidity of allenic hydrogens, to the predominance of the s-trans conformation, and to lithium complexation with both the carbonyl and the allene moieties. The relative stability of these enolates was examined with the use of semiempirical (MNDO) calculations which indicated that the lowest energy isomers are the (Z)-alkynolates. Both experimental and computational evidence suggest that the kinetic intermediate is the cumulenolate, while the thermodynamic enolate is the (Z)-alkynenolate.