Photoisomerization of Diazirine

Amrich, Michael J.; Bell, J. S.

doi:10.1021/ja01056a044

Cited by 56 publications

(21 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[17] Its levels increased at the beginning of the reaction and decreased along with the consumption of diazirine, due to secondary photolysis. It is interesting that the nearest homologues of diazirine -methyl-, ethyl-, and dimethyldiazirine -do not form stable diazo Scheme 1.…”

Section: Diazirinementioning

confidence: 99%

Valence Isomerization between Diazo Compounds and Diazirines

Korneev

2011

Eur J Org Chem

View full text Add to dashboard Cite

Diazo compounds and diazirines have been separately studied in detail and are widely used in research and for applied purposes. Although the mutual isomerization of these compounds was discovered 50 years ago, it has still been only modestly investigated. Meanwhile, this type of mutual transformation has to be taken into account on every occasion when one of these compounds is used or investigated. This review discusses all main cases of mutual isomerization between diazo compounds and diazirines with the goal of providing an impulse for its rational application, as well as describing the isomerism.

show abstract

Section: Diazirinementioning

confidence: 99%

Valence Isomerization between Diazo Compounds and Diazirines

Korneev

2011

Eur J Org Chem

View full text Add to dashboard Cite

show abstract

“…Aliphatic diazirines weakly absorb light at 350-370 nm and undergo competitive N 2 elimination and rearrangement to diazoalkanes (Scheme 1) [2][3][4]. Diazirinecontaining tags, such as 3-trifluoromethyl-3-phenyldiazirine [5] have been used for carbene generation and, when synthetically incorporated into complex molecules, can be used to probe protein-ligand interactions by creating cross linkages [6][7][8][9].…”

Section: Introductionmentioning

confidence: 99%

Electron Transfer Reduction of the Diazirine Ring in Gas-Phase Peptide Ions. On the Peculiar Loss of [NH₄O] from Photoleucine

Marek

Shaffer

Pepin

et al. 2014

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

Abstract. Electron transfer to gas-phase peptide ions with diazirine-containing amino acid residue photoleucine (L*) triggers diazirine ring reduction followed by cascades of residue-specific radical reactions. Upon electron transfer, substantial fractions of (GL*GGR +2H) +• cation-radicals undergo elimination of [NH O-labeled peptide ions and found to specifically involve the amide oxygen of the N-terminal residue. The structures, energies, and electronic states of the peptide radical species were elucidated by a combination of near-UV photodissociation experiments and electron structure calculations combining ab initio and density functional theory methods. Electron transfer reaching the ground electronic states of charge reduced (GL*GGR +2H) +• cation-radicals was found to reduce the diazirine ring. In contrast, backbone N−C α bond dissociations that represent a 60%-75% majority of all dissociations because of electron transfer are predicted to occur from excited electronic states.

show abstract

“…In the photodecomposition of diazirine to CH plus N 2 the diazirine-diazomethane isomerization has been suggested as a possible primary reaction channel [ 18,193, and such a process could involve the C-N stretching mode as the reaction COordinate. However, subsequent experimental evidence has failed to confirm this mechanism in either diazirine [20] or perfluorodiazirine [8,2 11.…”

Section: Resultsmentioning

confidence: 99%

Model for a three‐center decomposition reaction. I. Perfluorodiazirine

Tschuikow‐Roux¹,

Jung²

1975

Int J of Chemical Kinetics

View full text Add to dashboard Cite

A semiempirical approach has been used to evaluate rate parameters for a three-center decomposition reaction from the point of view of transition state theory, with perfluorodiazirine serving as the prototype molecule. Several activated complex models are considered in which the reaction coordinate is chosen as the 4 N C N bending mode. The consrraints imposed include the principle of concerted bond-order conservation in passing from the initial to the final state, and use is made of empirical bond order-bond length and bond order-force constant relationships. The geometric configuration of the transition state sought is one which conforms with the lowest energy path and is also consistent with the observed entropy of activation. The potential energy of activation is taken as the optimum difference in binding energies (based on the INDO method) between the transition and initial states, and the critical energy is obtained by applying a correction for the zero-point energy difference, derived from normal coordinate analysis. Satisfactory agreement is found in the case of the activated complex model for which the total bond order is conserved and bonds undergoing rupture are assigned a fractional bond order (FBO) of 2 / 3 , derived from the postulate (FBO) = a / B where a ( = 2 ) is the number of bonds breaking, and @( =3) is the number of bonds undergoing change in the ring opening.

show abstract

Photoisomerization of Diazirine

Cited by 56 publications

References 1 publication

Valence Isomerization between Diazo Compounds and Diazirines

Valence Isomerization between Diazo Compounds and Diazirines

Electron Transfer Reduction of the Diazirine Ring in Gas-Phase Peptide Ions. On the Peculiar Loss of [NH₄O] from Photoleucine

Model for a three‐center decomposition reaction. I. Perfluorodiazirine

Contact Info

Product

Resources

About

Photoisomerization of Diazirine

Cited by 56 publications

References 1 publication

Valence Isomerization between Diazo Compounds and Diazirines

Valence Isomerization between Diazo Compounds and Diazirines

Electron Transfer Reduction of the Diazirine Ring in Gas-Phase Peptide Ions. On the Peculiar Loss of [NH4O] from Photoleucine

Model for a three‐center decomposition reaction. I. Perfluorodiazirine

Contact Info

Product

Resources

About

Electron Transfer Reduction of the Diazirine Ring in Gas-Phase Peptide Ions. On the Peculiar Loss of [NH₄O] from Photoleucine