Photochemistry of cyclopropanes, methylenecyclopropanes, and vinylidenecyclopropanes

Mizuno, Kazuhiko; Ichinose, Nobuyuki; Yoshimi, Yasuharu

doi:10.1016/s1389-5567(00)00011-3

Cited by 45 publications

(31 citation statements)

References 177 publications

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“…The photochemistry of cyclopropane and its substituted derivatives has been studied extensively for its use in synthetic organic chemistry. [1][2][3] This moiety is often bonded to larger chromophores in organic synthesis and facilitated isomerization and ring-expansion 1 upon irradiation with deepultraviolet radiation (up to 6.7 eV). [4][5][6][7] As the smallest organic ring, the excited states of cyclopropane and the cyclopropyl radical have been of interest for many years, with previous studies focusing on vibronic coupling in the lowest-energy excited states.…”

Section: Introductionmentioning

confidence: 99%

Vacuum ultraviolet excited state dynamics of the smallest ring, cyclopropane. II. Time-resolved photoelectron spectroscopy and ab initio dynamics

Coates

Larsen

Forbes

et al. 2018

The Journal of Chemical Physics

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The vacuum-ultraviolet photoinduced dynamics of cyclopropane (C 3 H 6) were studied using timeresolved photoelectron spectroscopy (TRPES) in conjunction with ab initio quantum dynamics simulations. Following excitation at 160.8 nm, and subsequent probing via photoionization at 266.45 nm, the initially prepared wave packet is found to exhibit a fast decay (<100 fs) that is attributed to the rapid dissociation of C 3 H 6 to ethylene (C 2 H 4) and methylene (CH 2). The photodissociation process proceeds via concerted ring opening and CC bond cleavage in the excited state. Ab initio multiple spawning simulations indicate that ring-opening occurs prior to dissociation. The dynamics simulations were subsequently employed to simulate a TRPES spectrum, which was found to be in excellent agreement with the experimental result. On the basis of this agreement, the fitted time constants of 35 ± 20 and 57 ± 35 fs were assigned to prompt (i) dissociation on the lowest-lying excited state, prepared directly by the pump pulse, and (ii) non-adiabatic relaxation from higher-lying excited states that lead to delayed dissociation, respectively.

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Section: Introductionmentioning

confidence: 99%

Vacuum ultraviolet excited state dynamics of the smallest ring, cyclopropane. II. Time-resolved photoelectron spectroscopy and ab initio dynamics

Coates

Larsen

Forbes

et al. 2018

The Journal of Chemical Physics

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“…This rearrangement were found to be opposite those observed for similar methylenecyclopropane derivatives that usually lead to the cleavage at the C 2 OC 3 bond [3,7]. Accordingly, a singlet mechanism is proposed for the former photo rearrangements of vinylidenecyclopropanes, the main feature of which is the formation of an intermediate structure having a singlet 1,3-biradical character.…”

mentioning

confidence: 74%

“…However, even though the triplet state is lower in energy, photoirradiation often results in the formation of the higher-lying (but more reactive!) singlet structures [3].…”

Section: Zhanpeisov Et Almentioning

confidence: 99%

“…As can be expected, this is the least favorable route among all pathways considered because it occurs with simultaneous breakage of the C 1 OC 2 and C 2 OC 3 bonds. This also leads to the formation of highly reactive CR 2 , where R stands for either H or CH 3 . Thus, for example, the products formed in such a way lie about 83.5 and 75.3 kcal/mol higher in energy as compared to the precursor 1,1-diarylvinylidene-2,3-dimethyl-and 1,1-diarylvinylidene-2,2,3,3-tetramethylcyclopropanes, respectively.…”

Section: Zhanpeisov Et Almentioning

confidence: 99%

“…These highly strained cyclopropane-based systems can also be considered building blocks for more complex molecules. In past decades, the main body of investigations reported in the literature has been performed to understand the mechanism of the target bond cleavage in meth-ylenecyclopropanes [1][2][3]. At the same time, much less is known on vinylidenecyclopropanes although they represent the next nearest-neighbor homologous members of these unsaturated hydrocarbons [4,5].…”

mentioning

confidence: 99%

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C₁C₂ bond cleavage in vinylidenecyclopropanes: Theoretical density functional theory study

Zhanpeisov

Mizuno

Anpo

et al. 2003

Int J of Quantum Chemistry

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ABSTRACT:Density functional calculations at the B3LYP/6-31G* level were carried out to investigate the photo rearrangements in 1,1-diarylvinylidene-2,3-dimethyl-and 1,1-diarylvinylidene-2,2,3,3-tetramethylcyclopropanes. Among the five different routes considered, none except the one leading to the final products of butatriene derivatives (route 4) was found to be able to explain the experimental findings only. However, the route 4 points out on the involvement of the C 1 OC 2 bond cleavage in strained cyclopropane ring. Thus, a new mechanism that results in successive transformations was suggested to explain this distinct C 1 OC 2 bond cleavage in cyclopropane ring for both precursors leading to formation of butatriene derivatives. The results of calculations indicate that photochemistry of vinylidenecyclopropane derivatives is significantly different than in the case of methylenecyclopropane compounds.

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Allenic Hydrocarbons – Preparation and Use in Organic Synthesis

Hopf¹

2004

Modern Allene Chemistry

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Photochemistry of cyclopropanes, methylenecyclopropanes, and vinylidenecyclopropanes

Cited by 45 publications

References 177 publications

Vacuum ultraviolet excited state dynamics of the smallest ring, cyclopropane. II. Time-resolved photoelectron spectroscopy and ab initio dynamics

Vacuum ultraviolet excited state dynamics of the smallest ring, cyclopropane. II. Time-resolved photoelectron spectroscopy and ab initio dynamics

C₁C₂ bond cleavage in vinylidenecyclopropanes: Theoretical density functional theory study

Allenic Hydrocarbons – Preparation and Use in Organic Synthesis

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Photochemistry of cyclopropanes, methylenecyclopropanes, and vinylidenecyclopropanes

Cited by 45 publications

References 177 publications

Vacuum ultraviolet excited state dynamics of the smallest ring, cyclopropane. II. Time-resolved photoelectron spectroscopy and ab initio dynamics

Vacuum ultraviolet excited state dynamics of the smallest ring, cyclopropane. II. Time-resolved photoelectron spectroscopy and ab initio dynamics

C1C2 bond cleavage in vinylidenecyclopropanes: Theoretical density functional theory study

Allenic Hydrocarbons – Preparation and Use in Organic Synthesis

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C₁C₂ bond cleavage in vinylidenecyclopropanes: Theoretical density functional theory study