<b>Stereochemical Evidence of Bridged Radicals</b>

Skell, P. S.; Tuleen, David L.; Readio, P. D.

doi:10.1021/ja00901a038

Cited by 61 publications

(40 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…20. If so, this will be consistent with the Skell hypothesis for the origin of stereochemical control in such systems [96] [97]. The bond distances and angles for all three species are shown, along with the ab initio and DFT values for comparison.…”

Section: 23supporting

confidence: 79%

Ultrafast Electron Diffraction (UED). A New Development for the 4D Determination of Transient Molecular Structures

et al. 2003

View full text Add to dashboard Cite

With properly timed sequences of ultrafast electron pulses, it is now possible to image complex molecular structures in the four dimensions of space and time with resolutions of 0.01 ä and 1 ps, respectively. The new limits of ultrafast electron diffraction (UED) provide the means for the determination of transient molecular structures, including reactive intermediates and non-equilibrium structures of complex energy landscapes. By freezing structures on the ultrafast timescale, we are able to develop concepts that correlate structure with dynamics. Examples include structure-driven radiationless processes, dynamics-driven reaction stereochemistry, pseudorotary transition-state structures, and non-equilibrium structures exhibiting negative temperature, bifurcation, or selective energy localization in bonds. These successes in the studies of complex molecular systems, even without heavy atoms, and the recent development of a new machine devoted to structures in the condensed phase, establish UED as a powerful method for mapping out temporally changing molecular structures in chemistry, and potentially, in biology. This review highlights the advances made at Caltech, with emphasis on the principles of UED, its evolution through four generations of instrumentation (UED-1 to UED-4) and its diverse applications.

show abstract

Section: 23supporting

confidence: 79%

Ultrafast Electron Diffraction (UED). A New Development for the 4D Determination of Transient Molecular Structures

et al. 2003

View full text Add to dashboard Cite

show abstract

“…I/I000 of the rate that bromine does [15]: in essence, solubility and reactivity factors conspire together to retard the succinimidyl radical chain (Eq. (3)) and promote bromine atom chain propagation (Eq.…”

Section: The Recognition Of the Succinimidyl Radicalmentioning

confidence: 99%

Recent controversy on imidyl radical chemistry

Chow

Naguib

1984

Reviews of Chemical Intermediates

View full text Add to dashboard Cite

“…Table 1. It is difficult to ascertain the optical purity of this cornpound because of the discrepancy in published specific rotations (2,12,16,17). It does, however, seem reasonable to assume that it has the same optical purity as the starting alcohol, ciz., 100%.…”

Section: II Iiimentioning

confidence: 99%

The autoxidation of optically active 1-bromo-2-methylbutane

Howard¹,

Chenier²,

Holden³

1977

Can. J. Chem.

View full text Add to dashboard Cite

(+)-1-Bromo-2-methylbutane undergoes autoxidation at 1 atm of oxygen and 30 °C to give, after reduction with triphenylphosphine, 1-bromo-2-methyl-2-butanol with a (+) to (−) enantiomer ratio of 1.9 ± 0.2. The optically active 1-bromo-2-methyl-2-butyl radical is, therefore, partially trapped by oxygen at this pressure before it has time to completely racemize. The half-life for racemization of the preferred conformation is approximately 2 × 10−8 s−1 at 30 °C. At 100 atm of oxygen the yield of (+)-CH3CH2COH(CH3)CH2Br is >90% and the reaction appears to proceed with retention of configuration. A small percentage of (−)-1-bromo-2-methyl-2-butanol is, however, still produced, presumably by inversion of configuration.

show abstract

Stereochemical Evidence of Bridged Radicals

Cited by 61 publications

References 1 publication

Ultrafast Electron Diffraction (UED). A New Development for the 4D Determination of Transient Molecular Structures

Ultrafast Electron Diffraction (UED). A New Development for the 4D Determination of Transient Molecular Structures

Recent controversy on imidyl radical chemistry

The autoxidation of optically active 1-bromo-2-methylbutane

Contact Info

Product

Resources

About