Diphenylcyclopropenone, a three-membered analog of tropone

Vol'pin, M. E.; Koreshkov, Yu. D.; Kursanov, D.N.

doi:10.1007/bf00917720

Cited by 12 publications

(9 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since its first preparation in 1959, cyclopropenones received considerable attention due to their description as possible aromatic compounds . The discovery of the cyclopropenone-containing natural antibiotic penitricin, as well as cyclopropenone-based protease inhibitors, renewed interest in this class of cyclic ketones.…”

Section: Introductionmentioning

confidence: 99%

“…The discovery of the cyclopropenone-containing natural antibiotic penitricin, as well as cyclopropenone-based protease inhibitors, renewed interest in this class of cyclic ketones. The three-membered ring of cyclopropenones is constructed of formally sp 2 -hybridized carbon atoms but is, nevertheless, characterized by high thermal stability. , The chemical reactivity of cyclopropenones is dominated by two processes: 2 the nucleophilic ring opening, which results in the formation of acrylic acid derivatives, and the loss of carbon monoxide under high-temperature pyrolysis or in the presence of various catalysts. 1b, …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Mechanism of the Cyclopropenone Decarbonylation Reaction. A Density Functional Theory and Transient Spectroscopy Study

Poloukhtine

Popik

2006

J. Phys. Chem. A

View full text Add to dashboard Cite

The density functional theory analysis predicts that the thermal decarbonylation of cyclopropenones proceeds by the sequential and regioselective cleavage of both single bonds in a three-membered ring. The initial ring-opening process results in the formation of a reactive zwitterionic intermediate 6, which is separated from the free alkyne and carbon monoxide by a very low energy barrier. Femtosecond pump-probe transient absorption spectroscopy experiments showed that light-induced decarbonylation is also a stepwise process but apparently proceeds on the excited-state surface. The lifetime of the intermediate in the photodecarbonylation reaction is very short and is dependent on substitution and solvent polarity. Thus, bis-p-anisyl-substituted species decays with tau = 0.6 ps, bis-alpha-naphthyl-substituted intermediate has a lifetime of tau = 11 ps, while the bis(2-methoxy-1-naphthyl)-substituted analogue survives for 83 ps in chloroform and for 168 ps in argon-saturated methanol. The loss of carbon monoxide from these intermediates results in the formation of corresponding acetylenes in an electronically ground state. The addition of triplet quenchers does not affect the dynamics or outcome of the reaction.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Mechanism of the Cyclopropenone Decarbonylation Reaction. A Density Functional Theory and Transient Spectroscopy Study

Poloukhtine

Popik

2006

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…The preparation of the first cyclopropenone, diphenylcyclopropenone, was reported independently in 1959 by Breslow et al and Vol'pin et al . Cyclopropenones received considerable attention due to their possible description as aromatic compounds . The discovery of cyclopropenone-containing natural antibiotic penitricin, as well as cyclopropenone-based protease inhibitors, renewed interest in this class of cyclic ketones.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Photochemical Generation of a Triple Bond: Synthesis, Properties, and Photodecarbonylation of Cyclopropenones

2003

View full text Add to dashboard Cite

UV irradiation of alkyl-, aryl-, and heteroatom-substituted cyclopropenones results in the loss of carbon monoxide and the formation of quantitative yields of corresponding alkynes. The quantum yield of the photochemical decarbonylation reaction ranges from 20% to 30% for alkyl-substituted cyclopropenones to above 70% for the diphenyl- and dinaphthylcyclorpopenones. Rapid formation (<5 ns) and then a somewhat slower decay (ca. 40 ns) of an intermediate in this reaction was observed by using laser flash photolysis. The DFT calculations allowed us to identify this intermediate as a zwitterionic species formed by a cleavage of one of the carbon-carbon bonds of the cyclopropenone ring. The latter then rapidly loses carbon monoxide to produce the ultimate acetylenic product. Despite their high photoreactivity, cyclopropenones were found to be thermally stable compounds with the exception of hydroxy- and methoxy-substituted cyclopropenones. The latter undergo rapid solvolysis in hydroxylic solvents even at room temperature. The application of this reaction to the in situ generation of the enediyne structure was illustrated by the photochemical preparation of benzannulated enediyne 12.

show abstract

“…For the past few decades, significant advances have been made in the field of C–C bond activation, which is an intriguing process from both mechanistic and synthetic standpoints . As the smallest of the compounds exhibiting Hückel aromaticity, cyclopropenones are ideal candidates for C–C bond cleavage. , Because of their ambiphilic properties, cyclopropenones can serve as excellent 3C synthons, which provide wide utility in numerous chemical transformations. − Generally, there are two different modes for metal-catalyzed ring-opening of cyclopropenones, and β-carbon elimination is one of the elementary ways for cleavage of the C–C(O) bond (Scheme a) . However, few examples have been documented in this field, which represents a highly desirable but unmet goal.…”

mentioning

confidence: 99%