Chlorination of unsymmetrical sulfides

Tuleen, David L.; Stephens, Thomas

doi:10.1021/jo00838a009

Cited by 72 publications

(27 citation statements)

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“…The mixture was stirred for 30 min at room temperature. Afterwards a solution of 1‐Chlor‐1‐phenylsulfanyl‐5‐hexene (566 mg, 2.50 mmol)30 in THF (2 mL) was added and the reaction mixture was heated under reflux for 20 h. The reaction was stopped upon the addition of H 2 O followed by extraction of the aqueous layer with Et 2 O (2×). The combined organic layers were dried over MgSO 4 and the solvents were removed in vacuo.…”

Section: Methodsmentioning

confidence: 99%

Tin‐Free Radical Alkoxyamine Addition and Isomerization Reactions by Using the Persistent Radical Effect: Variation of the Alkoxyamine Structure

Molawi

Schulte

Siegenthaler

et al. 2005

Chemistry A European J

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Various C-centered radicals can efficiently be generated through thermal C-O-bond homolysis of alkoxyamines. This method is used to perform environmentally benign radical cyclization and intermolecular addition reactions. These alkoxyamine isomerizations and intermolecular carboaminoxylations are mediated by the persistent radical effect (PRE). In the paper, the effect of the variation of the alkoxyamine structure--in particular steric effects in the nitroxide moiety--on the outcome of the PRE mediated radical reactions will be discussed. Fourteen different nitroxides were used in the studies. It will be shown that reaction times can be shortened about 100 times upon careful tuning of the alkoxyamine structure. Activation energies for the C-O-bond homolysis of the various alkoxyamines are provided. The kinetic data are used to explain the reaction outcome of the PRE-mediated processes.

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Section: Methodsmentioning

confidence: 99%

Tin‐Free Radical Alkoxyamine Addition and Isomerization Reactions by Using the Persistent Radical Effect: Variation of the Alkoxyamine Structure

Molawi

Schulte

Siegenthaler

et al. 2005

Chemistry A European J

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“…Based on results from Ingold and Beckwith on the stabilization of nitroxides by intermolecular hydrogen bonding, [17] we decided to prepare new nitroxides capable of intramolecular hydrogen bonding (23). [29] In addition to decreasing the trapping rate of the nitroxide with C-centered radicals, the hydrogen bonding should also influence the rate of C À O bond homolysis (late transition state).…”

mentioning

confidence: 99%

Tin-Free Radical Cyclization Reactions Using the Persistent Radical Effect

Studer¹

2000

Angew. Chem. Int. Ed.

140

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“…( i ) reaction will go into the side chain bearing the most acidic a-H atoms (13) and (ii) reaction will go into the side chain which is best able to support positive charge (14). We have argued ( I ) that the first proposal is inconsistent with the reaction shown in eq.…”

mentioning

confidence: 99%

Regiochemistry and reactivity in the chlorination of sulfides

Hancock¹,

Hardstaff²,

Johns³

et al. 1983

Can. J. Chem.

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Huheey's original method for the calculation of substituent electronegativities is modified so that isomeric groups have different electronegativities. The modified form of Huheey's method is then employed to show that our previously published method for anticipating regiochemistry in asymmetric sulfide chlorinations, i.e., ΔXP calculations for the α and α′ substituents in the sulfide substrates, is successful in all fifty known cases. A new reactivity function (RP) is defined, for the sulfenium ion intermediates, which permits one to anticipate when substrates become inert to chlorine in exhaustive chlorinations conducted in aprotic media.

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Chlorination of unsymmetrical sulfides

Cited by 72 publications

References 0 publications

Tin‐Free Radical Alkoxyamine Addition and Isomerization Reactions by Using the Persistent Radical Effect: Variation of the Alkoxyamine Structure

Tin‐Free Radical Alkoxyamine Addition and Isomerization Reactions by Using the Persistent Radical Effect: Variation of the Alkoxyamine Structure

Tin-Free Radical Cyclization Reactions Using the Persistent Radical Effect

Regiochemistry and reactivity in the chlorination of sulfides

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