Some guidelines for radical reactions

Beckwith, A. L. J.; Easton, Christopher J.; Serelis, Algirdas K.

doi:10.1039/c39800000482

Cited by 232 publications

(118 citation statements)

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“…These are based on the assumption that the preferred transition state geometry resembles the most favorable cyclohexane chairlike conformation (23). Based on these studies, it has been established that, for simple monoalkyl substituted 5-hexenyl cyclizations, cis dialkylcyclopentanes predominate with 1-and 3-substituted systems.…”

Section: Resultsmentioning

confidence: 99%

Free-radical based cycloalkanol synthesis and annulation from thioacetal precursors

Yadav¹,

Fallis²

1991

Can. J. Chem.

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A general procedure for the synthesis of diverse cyclopentanols via free-radical cyclization of unsaturated 1,3-oxathiolanes and I ,3-oxathiolan-5-ones is described. The scope of these reactions, including preliminary rate studies that indicate that the 1,3-oxathiolan-5-ones cyclize at a useful rate (I .4 X lo6 M-I S -I at 80°C), has been examined. This permits the rapid assembly, by intramolecular annulation, of various additional ring systems, including bicyclo[3.

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Section: Resultsmentioning

confidence: 99%

Free-radical based cycloalkanol synthesis and annulation from thioacetal precursors

Yadav¹,

Fallis²

1991

Can. J. Chem.

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“…As stated by Beckwith and coworkers [6], P-fission is favoured when the bond concerned lies close to the plane of an adjacent semi-occupied orbital (trans-antiperiplanar relationship). In our system C(* = *), where a strong conformational preference is recognizable, the direction of ring opening would conform to this guideline.…”

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confidence: 88%

Fe(II)‐Induced Fragmentation Reaction of γ‐Hydroperoxy‐α,β‐enones. Part 1. Synthesis of 13(14→8)‐abeo‐Steroids

Canonica

Danieli

Lesma

et al. 1987

Helvetica Chimica Acta

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Some steroidal analogues embodying the hitherto unknown 13( 14+X)-abeo skeleton have been synthesized by Fe(I1)-induced rearrangement (tandem b-fissionlreductive alkylation) of 14a -hydroperoxy-7-en-6-ones. The configurational assignment was made by thorough analysis of NMR spectra; the structure of one of the products was unambiguously assessed by X-ray single-crystal analysis.Introduction. -Recently, we have briefly reported [ 11 that irradiation of the insectmoulting hormone 20-hydroxyecdysone ( = crustecdysone; 1) [2] in H,O through Pyrex yielded, in addition to the reduction products 2 and 3 containing intact steroidal framework, the unprecedented ketone 4 and the cyclobutanol5. Our attention was focused on

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“…The radical rearrangement rate is assumed to be constant under all reaction conditions. However, for a ring-closure-type radical clock, we [19] were able to show that complexation of the double bond of the intermediate hex-1-en-6-yl radical [20] to a lithium cation decreases the calculated activation barrier for the ring-closing rearrangement significantly. This effect is supported indirectly by recent work of Michl and co-workers, [21,22] who showed that "naked" lithium cations have a catalyzing effect on the radical polymerization of terminal olefins, in accord with a proposal made 20 years ago on the basis of ab initio calculations [23] and a recent more-detailed study at higher theoretical levels.…”

Section: Introductionmentioning

confidence: 95%

The Effect of a Complexed Lithium Cation on a Norcarane‐Based Radical Clock

Jäger

Hennemann

Clark

2009

Chemistry A European J

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Density-functional theory (DFT) and ab initio calculations have been used to investigate the effect of a complexed lithium cation on the radical-clock rearrangement of the 2-norcaranyl radical to the 3-cyclohexenylmethyl radical. As found earlier for ring-closing radical clocks, complexation with a metal ion leads to a significant lowering of the barrier to rearrangement. DFT calculations on a model for the norcaranyl clock in cytochrome P450 confirm the two-state reactivity proposal of Shaik et al. and indicate that the porphyrin exerts little or no electrostatic effect on the rearrangement barrier.

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Some guidelines for radical reactions

Cited by 232 publications

References 3 publications

Free-radical based cycloalkanol synthesis and annulation from thioacetal precursors

Free-radical based cycloalkanol synthesis and annulation from thioacetal precursors

Fe(II)‐Induced Fragmentation Reaction of γ‐Hydroperoxy‐α,β‐enones. Part 1. Synthesis of 13(14→8)‐abeo‐Steroids

The Effect of a Complexed Lithium Cation on a Norcarane‐Based Radical Clock

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