Electrochemical study of the formation of cyclopropanes from gem-dihalocompounds and alkenes catalyzed by copper 1,10-phenanthroline complexes

Léonel, Éric; Dolhem, Eric; Devaud, Marguerite; Paugam, Jean Paul; Nédélec, Jean‐Yves

doi:10.1016/s0013-4686(97)85489-8

Cited by 7 publications

(4 citation statements)

References 24 publications

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“…1,3-Dihalo-1,3-diarylpropanes are important intermediates in the preparation of arylcyclopropane, pyrazolidine, and centrohexaindane . The bromo analogues can also be utilized in Suzuki coupling reactions .…”

Section: Resultsmentioning

confidence: 99%

Lewis Acid Mediated Reactions of Aldehydes with Styrene Derivatives: Synthesis of 1,3-Dihalo-1,3-diarylpropanes and 3-Chloro-1,3-diarylpropanols

Kabalka

et al. 2005

J. Org. Chem.

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[reaction: see text] The reactions of aryl aldehydes with styrene derivatives, mediated by various boron Lewis acids, were investigated. 1,3-Dihalo-1,3-diarylpropanes were obtained in high yields with boron trihalides, while 3-chloro-1,3-diarylpropanols were obtained in good to excellent yields with phenylboron dichloride. Reactions involving nonenolizable aliphatic aldehydes, trans-cinnamaldehyde, and beta-substituted styrenes were also investigated for the first time.

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Section: Resultsmentioning

confidence: 99%

Lewis Acid Mediated Reactions of Aldehydes with Styrene Derivatives: Synthesis of 1,3-Dihalo-1,3-diarylpropanes and 3-Chloro-1,3-diarylpropanols

Kabalka

et al. 2005

J. Org. Chem.

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“…Br (R = MeO 2 C) at the double bond. 75 The radical intermediate is subsequently reduced to the corresponding anion, no transformations into carbene or alkylcopper intermediates being observed. In the reactions with other gem-dihalides, the products are formed by the chain mechanism involving addition.…”

Section: Homocoupling Of Organic Dihalidesmentioning

confidence: 99%

“…73,74 Electrochemical reductive coupling of some gem-dihalides, in particular, of dimethyl dibromomalonate in the presence of the copper complex with 1,10-phenanthroline and a sacrificial copper anode gave rise to cyclopropanes. 75 Studies by cyclic voltammetry and chronoamperometry showed that reduction of dimethyl dibromomalonate with the Cu(I) complex is a catalytic process, which is kinetically controlled by the rate of concerted electron transfer and cleavage of the carbon7bromine bond. In the presence of styrene, cyclopropane is formed through the addition of R 2 C…”

Section: Homocoupling Of Organic Dihalidesmentioning

confidence: 99%

Metal complex catalysis in organic electrosynthesis

Budnikova¹

2002

Russ. Chem. Rev.

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Data on the use of electrochemically generated metal Data on the use of electrochemically generated metal complex catalysts in organic synthesis are analysed, systematised complex catalysts in organic synthesis are analysed, systematised and generalised. The considerable potential of organic electro-and generalised. The considerable potential of organic electrochemistry is shown. Some electrochemical methods provide chemistry is shown. Some electrochemical methods provide advantages in the synthesis of compounds where conventional advantages in the synthesis of compounds where conventional chemical methods fail, are experimentally complicated or have chemical methods fail, are experimentally complicated or have environmental limitations. Particular attention is given to the environmental limitations. Particular attention is given to the mechanisms of electrocatalytic reactions. The bibliography mechanisms of electrocatalytic reactions. The bibliography includes 333 references includes 333 references. .

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“…Copper−phenanthroline complexes have attracted great interest over the past years due to their potential in technologically important applications, such as solar energy conversion, molecular sensing, and photocatalysis. , Of particular interest is the capability of Cu(I)−phenanthroline complexes to act as probes for biological structures. − Owing to the large reducing tendency of the metal center, Cu(I) complexes display charge-transfer transitions in the form of metal-to-ligand charge-transfer (MLCT) bands, which occur in the visible region of the electronic absorption spectrum . The presence of low-lying MLCT excited states causes the luminescence of these complexes to become very sensitive to their environment, making them ideal probes for studying protein structures and nucleic acid interactions.…”

Section: Introductionmentioning

confidence: 99%

The Effect of Ligand Constraints on the Metal-to-Ligand Charge-Tranfer Relaxation Dynamics of Copper(I)−Phenanthroline Complexes: A Comparative Study by Femtosecond Time-Resolved Spectroscopy

2003

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Two geometrically constrained Cu(I)-monophenanthroline complexes were investigated spectroscopically to study the effects that ligand constraints have on the excited-state dynamics of copper-phenanthroline complexes. Room temperature steady-state absorption and emission spectra were obtained for the two complexes and time-resolved fluorescence spectra of the Cu(I) complexes in dichloromethane were collected using time-correlated single photon counting. The effect of the ligands on the excited-state dynamics of the two complexes was monitored by femtosecond pump-probe spectroscopy. Transient absorption spectroscopy with femtosecond resolution enabled the direct observation of the relaxation in the photoinduced metal-toligand charge-transfer (MLCT) state of the complexes, where the tetrahedral Franck-Condon Cu(II) complex undergoes vibrational relaxation to form the energetically favorable square planar conformation. The flattening relaxation was found to have two lifetime components of 8-10 and 40-52 ps for the rearrangement of the 1:1 copper-phenanthroline complexes, which is likely related to the flattening around the metal center and the subsequent rearrangement of the methylphenyl-pyrazole backbone according to the more planar conformation, respectively. The excited-state dynamics correlate with the measured UV-vis absorption and emission properties of the complexes and are discussed in the light of steric constraints on the photophysics of the Cu(I)-monophenanthroline complexes. The higher quantum yield, longer emission lifetime, and faster relaxation dynamics of the dimethyl-substituted pyrazole-based complex compared with the unmethylated analogue agree with the steric arguments that in a 1:1 ligand framework, addition of alkyl substituents in the ligand hinders the flattening relaxation. This investigation is complementing photophysical studies performed over the past two decades on the effect of substitutents on the photophysics of the structurally related 1:2 Cu(I)-phenanthroline complexes by providing a time-resolved spectroscopic observation of the excited-state relaxation in geometrically constrained Cu(I)-phenanthroline complexes following the photoinduced MLCT.

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Electrochemical study of the formation of cyclopropanes from gem-dihalocompounds and alkenes catalyzed by copper 1,10-phenanthroline complexes

Cited by 7 publications

References 24 publications

Lewis Acid Mediated Reactions of Aldehydes with Styrene Derivatives: Synthesis of 1,3-Dihalo-1,3-diarylpropanes and 3-Chloro-1,3-diarylpropanols

Lewis Acid Mediated Reactions of Aldehydes with Styrene Derivatives: Synthesis of 1,3-Dihalo-1,3-diarylpropanes and 3-Chloro-1,3-diarylpropanols

Metal complex catalysis in organic electrosynthesis

The Effect of Ligand Constraints on the Metal-to-Ligand Charge-Tranfer Relaxation Dynamics of Copper(I)−Phenanthroline Complexes: A Comparative Study by Femtosecond Time-Resolved Spectroscopy

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