Photocyclization of propenes to cyclopropanes novel phenyl and hydrogen migrations in π,π systems

Griffin, G. W.; Marcantonio, Arnold F.; Kristinsson, H.; Petterson, R. C.; Irving, Charles S.

doi:10.1016/s0040-4039(01)89240-6

Cited by 36 publications

(17 citation statements)

References 11 publications

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“…E.g., hydrocarbon 35 undergoes hydrogen and phenyl migration upon photoexcitation (Scheme 8, reaction A). [117][118][119] Indane derivative 35 is thus transformed into unstable isoindane 36, which evolves in the S 0 state to 37, isomeric to reactant 35. The formation of the unstable o-xylylene intermediate 36 has been confirmed through NMR spectroscopy at À70 1C.…”

Section: Photochemical Formation Of Ortho-xylylenesmentioning

confidence: 99%

The excited state antiaromatic benzene ring: a molecular Mr Hyde?

2015

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The antiaromatic character of benzene in its first ππ* excited triplet state (T1) was deduced more than four decades ago by Baird using perturbation molecular orbital (PMO) theory [J. Am. Chem. Soc. 1972, 94, 4941], and since then it has been confirmed through a range of high-level quantum chemical calculations. With focus on benzene we now first review theoretical and computational studies that examine and confirm Baird's rule on reversal in the electron count for aromaticity and antiaromaticity of annulenes in their lowest triplet states as compared to Hückel's rule for the ground state (S0). We also note that the rule according to quantum chemical calculations can be extended to the lowest singlet excited state (S1) of benzene. Importantly, Baird, as well as Aihara [Bull. Chem. Soc. Jpn. 1978, 51, 1788], early put forth that the destabilization and excited state antiaromaticity of the benzene ring should be reflected in its photochemical reactivity, yet, today these conclusions are often overlooked. Thus, in the second part of the article we review photochemical reactions of a series of benzene derivatives that to various extents should stem from the excited state antiaromatic character of the benzene ring. We argue that benzene can be viewed as a molecular "Dr Jekyll and Mr Hyde" with its largely unknown excited state antiaromaticity representing its "Mr Hyde" character. The recognition of the "Jekyll and Hyde" split personality feature of the benzene ring can likely be useful in a range of different areas.

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Section: Photochemical Formation Of Ortho-xylylenesmentioning

confidence: 99%

The excited state antiaromatic benzene ring: a molecular Mr Hyde?

2015

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“…. (12) From ( 12) one-center integrals arise of the type <iVc,[f7|iYc.) -r (Pz.Cblf 7|P"lCb> -r (13) and the sum in eq 12 does not equal 0.…”

Section: T H Imentioning

confidence: 99%

Spectroscopy of phenylcyclopropanes and phenylethanes. Unusual emissions from phenylcyclopropanes

Becker¹,

Edwards²,

Bost³

et al. 1972

J. Am. Chem. Soc.

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We have applied single determinant ab initio molecular orbital theory to the description of internal rotation in vinylcyclopropane and vinylcyclobutane. Using the minimal STO-3G basis we find the two molecules to be most stable in their s-trans forms but also predict both to possess flat secondary s-cis and gauche minima. Further investigation on vinylcyclopropane with the extended 4-31G basis set confirms the gauche minimum but places doubt on the stability of the s-cis structure. Substitution on the vinyl group in vinylcyclopropane by -

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“…When the glass was warmed, the spiro dimer 5 was formed. Irradiation of 1 (X > 345 nm) at 77 K resulted in formation of benzocyclobutene(9). Although there is one 9.…”

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confidence: 99%

o-Xylylenes and isoindenes as reaction intermediates

McCullough¹

1980

Acc. Chem. Res.

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After being largely ignored for many years, the simple structures o-xylylene (1) and isoindene (2) (also called o-quinodimethanes) and their derivatives are now under active investigation from theoretical, physical, physical organic, and synthetic organic viewpoints.The earliest report in which an o-xylylene structure was implicated was the reaction of , , ', '-tetrabromo-o-xylene with iodide ion to give 1,2-dibromobenzocyclobutene.1,2 This assignment was confirmed

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Photocyclization of propenes to cyclopropanes novel phenyl and hydrogen migrations in π,π systems

Cited by 36 publications

References 11 publications

The excited state antiaromatic benzene ring: a molecular Mr Hyde?

The excited state antiaromatic benzene ring: a molecular Mr Hyde?

Spectroscopy of phenylcyclopropanes and phenylethanes. Unusual emissions from phenylcyclopropanes

o-Xylylenes and isoindenes as reaction intermediates

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