Oxygen and sulfur methylation of ambident p-toluenesulfinate anion

Meek, John S.; Fowler, Joanna S.

doi:10.1021/jo01273a014

Cited by 93 publications

(29 citation statements)

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“…As reported in the literature [35,36,37], we observed formation of β-ketosulfones rather than β-ketosulfinate esters. An aqueous solution of sodium benzene sulfinate and the corresponding 2-bromoacetophenone was irradiated at 500 W, 100 °C in a microwave oven for 45 min to give sulfones 1 – 4 in good yields (61–92%) (Scheme 1).…”

Section: Resultssupporting

confidence: 86%

Manganese(III) Acetate-mediated Oxidative Cyclization of a-Methylstyrene and trans-Stilbene with b-Ketosulfones

et al. 2013

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A convenient microwave irradiation protocol was utilized for the synthesis of β-ketosulfones 1–5 in good yields. These sulfones reacted with alkenes through a radical oxidative cyclization mediated by Mn(OAc)3. Dihydrofurans 6–10 were obtained in moderate to good yields starting from 1,1-disubstituted alkenes. Dihydrofurans 11–15 were synthesized in moderate yields and unexpected cyclopropanes 16–19 were obtained in low yields starting from 1,2-disubstituted alkenes. This protocol offers access to various dihydrofurans which could be tested for their antiparasitic potential.

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Section: Resultssupporting

confidence: 86%

Manganese(III) Acetate-mediated Oxidative Cyclization of a-Methylstyrene and trans-Stilbene with b-Ketosulfones

et al. 2013

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“…[143] On the other hand, Meek and Fowler observed concomitant S and O attack in reactions of p-toluenesulfinate anions with various methylating agents ( Table 7). [154] As an interconversion between the resulting methyl sulfinic esters and the isomeric methyl sulfones was shown not to occur under the reaction conditions, the product ratios given in Table 7 are the result of kinetic control.…”

Section: Enolate Anionsmentioning

confidence: 95%

Farewell to the HSAB Treatment of Ambident Reactivity

Mayr¹,

Breugst²,

Ofial³

2011

Angew Chem Int Ed

264

211

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The concept of hard and soft acids and bases (HSAB) proved to be useful for rationalizing stability constants of metal complexes. Its application to organic reactions, particularly ambident reactivity, has led to exotic blossoms. By attempting to rationalize all the observed regioselectivities by favorable soft-soft and hard-hard as well as unfavorable hard-soft interactions, older treatments of ambident reactivity, which correctly differentiated between thermodynamic and kinetic control as well as between different coordination states of ionic substrates, have been replaced. By ignoring conflicting experimental results and even referring to untraceable experimental data, the HSAB treatment of ambident reactivity has gained undeserved popularity. In this Review we demonstrate that the HSAB as well as the related Klopman-Salem model do not even correctly predict the behavior of the prototypes of ambident nucleophiles and, therefore, are rather misleading instead of useful guides. An alternative treatment of ambident reactivity based on Marcus theory will be presented.

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“…Table 2, entry 1 shows that the spirodiepoxide reacts with sodium benzenesulfinate to give the sulfone. 8 No O -alkylation was observed in this case. Approximately stoichiometric sodium trifluoroethoxide adds efficiently (Table 2, entry 2), however, trifluoroethanol does not add to the spriodiepoxide under neutral conditions even in large excess, in contrast to water and other alcohols.…”

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confidence: 65%