75107-77-6

Upstream product

• 75107-85-6 (E)-2,2,4-Trimethyl-5-phenyl-pent-4-enoic acid ethyl ester 
• 1504-58-1 3-Phenyl-2-propyn-1-ol 
• 676-58-4 methylmagnesium chloride 
• 197963-29-4 2,2-dimethyl-5-phenylpent-4-ynal 
• 495414-11-4 (Z)-(3-bromo-1-iodo-2-methylprop-1-enyl)benzene 
• 253284-33-2 (Z)-3-iodo-2-methyl-3-phenylprop-2-en-1-ol 
• 495414-10-3 (Z)-5-iodo-2,2,4-trimethyl-5-phenyl-4-pentenenitrile 

Relevant academic research and scientific papers

Solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes: access to cyclopentenones and dihydropyranols

Divergent synthesis is a powerful strategy for the fast assembly of different molecular scaffolds from identical starting materials. We describe here a solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes with sulfonyl chlorides for the direct construction of highly functionalized cyclopentenones and dihydropyranols that widely exist in bioactive molecules and natural products. Density functional theory calculations suggest that a uniqueN,N-dimethylacetamide-assisted 1,2-hydrogen transfer of alkoxy radicals is responsible for the cyclopentenone formation, whereas a C-C cleavage accounts for the selective production of dihydropyranols in acetonitrile and water at 50 °C. Given the simple and mild reaction conditions, excellent functional group compatibility, forming up to four chemical bonds, and tunable selectivity, it may find wide applications in synthetic chemistry.

Migratory Aptitudes in Rearrangements of Destabilized Vinyl Cations

The Lewis acid-promoted generation of destabilized vinyl cations from β-hydroxy diazo ketones leads to an energetically favorable 1,2-shift across the alkene followed by an irreversible C-H insertion to give cyclopentenone products. This reaction sequence overcomes typical challenges of counter-ion trapping and rearrangement reversibility of vinyl cations and has been used to study the migratory aptitudes of nonequivalent substituents in an uncommon C(sp2) to C(sp) vinyl cation rearrangement. The migratory aptitude trends were consistent with those observed in other cationic rearrangements; the substituent that can best stabilize a cation more readily migrates. However, density functional theory calculations show that the situation is more complex. Selectivity in the formation of one conformational isomer of the vinyl cation and facial selective migration across the alkene due to an electrostatic interaction between the vinyl cation and the adjacent carbonyl oxygen work in concert to determine which group migrates. This study provides valuable insight into predicting migration preferences when applying this methodology to the synthesis of structurally complex cyclopentenones that are differentially substituted at the α and β positions.

Carbopalladation of nitriles: Synthesis of benzocyclic ketones and cyclopentenones via Pd-catalyzed cyclization of ω-(2-iodoaryl)alkanenitriles and related compounds

An efficient procedure for the synthesis of 2,2-disubstituted benzocyclic ketones by intramolecular carbopalladation of nitriles has been developed. The cyclization of substituted 3-(2-iodoaryl)-propanenitriles affords indanones in high yields. The reaction is compatible with a wide variety of functional groups. This methodology has been extended to the synthesis of tetralones and cyclopentenones.

A DIRECT THREE-CARBON ANNELATION TO CYCLOPENTENONE DERIVATIVES

Cyclopentenone derivatives were prepared by three-carbon alkylation followed by cyclisation of the ester.