Synthesis, chemical trapping and dimerization of tricyclo[3.3.0.03,7]oct-1(5)-ene, the consummate member of a series of pyramidalized alkenes

Camps, Pelayo; Luque, F. Javier; Orozco, Modesto; Pérez, F.; Vázquez, Santiago

doi:10.1016/0040-4039(96)01967-3

Cited by 32 publications

(8 citation statements)

References 14 publications

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“…The configuration of all of these compounds was clearly established by spectroscopic studies and, for compounds 8 , 9 , and 10 , confirmed by X‐ray diffraction analysis (see the Supporting Information). Compound 10 was irradiated in a quartz reactor by using a 125 W medium‐pressure mercury lamp in pentane3c or in a 1:1 benzene/acetone7 mixture at different reaction times (till 24 h). Due to solubility problems, compound 11 was irradiated under similar conditions but only in a 1:1 benzene/acetone mixture.…”

Section: Resultsmentioning

confidence: 99%

“…Selective hydrogenation of the tetraene 17 led to the diene 18 (Scheme ). Irradiation of compound 17 (quartz reactor, 125 W medium‐pressure mercury lamp in pentane3c or in a 1:1 benzene/acetone7 mixture) at different reaction times (till 4 h) led to degradation products in which the olefinic protons had disappeared. GC‐MS showed the presence, among others, of dihydro and tetrahydro compounds.…”

Section: Resultsmentioning

confidence: 99%

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Short Access to Belt Compounds with Spatially Close CC Bonds and Their Transannular Reactions

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Gómez

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et al. 2015

Chemistry A European J

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Two domino Diels-Alder adducts were obtained from 3,7-bis(cyclopenta-2,4-dien-1-ylidene)-cis-bicyclo[3.3.0]octane and dimethyl acetylenedicarboxylate or N-methylmaleimide under microwave irradiation. From the first adduct, a C20H24 diene with C2v symmetry was obtained by Zn/AcOH reduction, hydrolysis, oxidative decarboxylation, and selective hydrogenation. Photochemical [2+2] cycloaddition of this diene gave a thermally unstable cyclobutane derivative, which reverts to the diene. However, both the diene and the cyclobutane derivatives could be identified by X-ray diffraction analysis upon irradiation of the diene crystal. New six-membered rings are formed upon the transannular addition of bromine or iodine to the diene. The N-type selectivity of the addition was examined by theoretical calculations, which revealed the distinct susceptibility of the doubly bonded carbon atoms to the bromine attack.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Short Access to Belt Compounds with Spatially Close CC Bonds and Their Transannular Reactions

Camps

Gómez

Otermin

et al. 2015

Chemistry A European J

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“…Pyramidalized alkenes are molecules that contain a double bond in which the two π-carbons and their four substituents are not coplanar or it can derive from the geometric constraints of polycyclic olefins such as Wiberg's tricyclo[4.2.2.2 2,5 ]dodeca-1,5-diene ( 2 ), Prinzbach's substituted seco-diene ( 3 ), or Camps' tricyclo[3.3.0.0 3,7 ]oct-1(5)-ene ( 4 ), , as shown in Scheme . All four of these compounds contain double bonds that are significantly, and (for compounds 1 , 2 , and 4 ) because of their symmetry, identically pyramidalized syn at the affected alkene carbon atoms.…”

Section: Introductionmentioning

confidence: 99%

“…The reactivity of such distorted alkenes, as might be expected, is generally enhanced, with this reactivity being reflected by instability in air, rapid dimerization reactions, or in situ Diels−Alder reactions with various 1,3-dienes. For example, the formation of such distorted alkenes as 4 is deduced on the basis of the formation of its dimer, as shown in Scheme . The structural parameters of such highly reactive alkenes can only be estimated computationally, as was the case for 4 .…”

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confidence: 99%

A Highly Pyramidalized Cage Alkene Formed via the Double Diels−Alder Cycloaddition of syn-4,5,13,14-Bis(dehydro)octafluoroparacyclophane to Anthracene

et al. 2005

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[reaction: see text] A double Diels-Alder reaction of the formal syn-bis(dehydro)octafluoroparacyclophane with anthracene leads to formation of a novel cage compound that contains a highly pyramidal double bond. The measures of pyramidality of this double bond constitute what appear to be the highest combined values of psi and phi (34.3 degrees and 33.5 degrees, respectively) yet reported to have been determined by X-ray crystallography. This cage compound, although stable indefinitely as a crystalline compound in air, exhibits the high reactivity with both triplet and singlet O2 in solution that is characteristic of such highly pyramidal pi systems.

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“…An example of the former type of diene is provided by tricyclo[4.2.2.2 2,5 ]dodecadiene-1(2),5(6) ( 3 ), and pentacyclo [8.2.1.1 2,5 1. 4,7 1 8,11 ]hexadeca-1,7-diene ( 4a ) and its 4,5,10,11-tetramethyl derivative 4b provided examples of the latter. To demonstrate the existence of the predicted difference in the π-orbital energies in 3 and 4 , we have recorded the He(I) photoelectron (PE) spectra of 4a and 4b and compared the spectra with that of 3 …”

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π−π-Interactions in Pentacyclo- [8.2.1.1.^2,51.^4,71^8,11]hexadeca-1,7-diene

et al. 1998

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If two π-systems, such as two triple or two double bonds, are separated by ethano or propano bridges, a considerable difference between the energy splitting of the molecular π orbitals is encountered. This difference is apparent in comparing the photoelectron spectra of 1,5cyclooctadiyne (1) and 1,6-cyclodecadiyne (2). 1 The splitting of the ionization energies of the "in-plane" π-orbitals in these diynes was found to be 0.4 eV for 1 and 1.5 eV for 2. 1 A similar difference is expected in dienes in which the double bonds are connected by four ethano and four propano bridges. An example of the former type of diene is provided by tricyclo[4.2.2.2 2,5 ]dodecadiene-1(2),5(6) (3), 2 and pentacyclo [8.2.1.1 2,5 1. 4,7 1 8,11 ]hexadeca-1,7-diene (4a) 3 and its 4,5,10,11-tetramethyl derivative 4b 4 provided examples of the latter. To demonstrate the existence of the predicted difference in the π-orbital energies in 3 and 4, we have recorded the He(I) photoelectron (PE) spectra of 4a and 4b and compared the spectra with that of 3. 5 The PE spectrum of 4a ( Figure 1) shows two bands at 7.43 and 8.97 eV (see Table 1) which are well separated from strongly overlapping bands at higher energies. The PE spectrum of 4b looks very similar, and the first two bands appear at 7.32 and 8.79 eV.To interpret the PE spectra of 4a and 4b, we have carried out quantum chemical calculations on 4a. The geometry of 4a was optimized in D 2h symmetry at the Hartree-Fock level of theory, using the 6-31G* basis set. 6 A frequency calculation showed that the optimized D 2h geometry is a minimum on the potential energy surface for 4a. The predicted ionization energies were obtained, both from application of Koopmans's theorem 7 and by ∆SCF and ∆MP2 calculations (see Table 1). In the ∆SCF energy calculations we used the RHF method for the neutral molecule, and the UHF methology for the radical cation and its excited states. Thus, ∆MP2 uses the RMP2 method for 4a but its unrestricted version (UMP2) for the cations. All these single-point calculations were carried out at the RHF geometry of the neutral molecule 4a. The electronic structure of 4a was further investigated by partitioning the interactions between the localized π bonds into those through-space (TS) and those through-bond (TB). 8 We make use of a methodology, first suggested by Heilbronner and Schmelzer, 9 which is based on the Fock matrix in a localized basis. For a quantitative treatment we applied the procedure of Imamura et al. 10 It is based on subsequent diagonalization steps of those parts of the Fock matrix which correspond to the relevant localized orbitals. As a

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Synthesis, chemical trapping and dimerization of tricyclo[3.3.0.03,7]oct-1(5)-ene, the consummate member of a series of pyramidalized alkenes

Cited by 32 publications

References 14 publications

Short Access to Belt Compounds with Spatially Close CC Bonds and Their Transannular Reactions

Short Access to Belt Compounds with Spatially Close CC Bonds and Their Transannular Reactions

A Highly Pyramidalized Cage Alkene Formed via the Double Diels−Alder Cycloaddition of syn-4,5,13,14-Bis(dehydro)octafluoroparacyclophane to Anthracene

π−π-Interactions in Pentacyclo- [8.2.1.1.^2,51.^4,71^8,11]hexadeca-1,7-diene

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Synthesis, chemical trapping and dimerization of tricyclo[3.3.0.03,7]oct-1(5)-ene, the consummate member of a series of pyramidalized alkenes

Cited by 32 publications

References 14 publications

Short Access to Belt Compounds with Spatially Close CC Bonds and Their Transannular Reactions

Short Access to Belt Compounds with Spatially Close CC Bonds and Their Transannular Reactions

A Highly Pyramidalized Cage Alkene Formed via the Double Diels−Alder Cycloaddition of syn-4,5,13,14-Bis(dehydro)octafluoroparacyclophane to Anthracene

π−π-Interactions in Pentacyclo- [8.2.1.1.2,51.4,718,11]hexadeca-1,7-diene

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π−π-Interactions in Pentacyclo- [8.2.1.1.^2,51.^4,71^8,11]hexadeca-1,7-diene