Sulfonyl transfer mechanism in C–S coupling of phenylmagnesium bromide with phenyl arenesulfonates

Eroğlu, Fatma; Kâhya, Didem; Erdık, Ender

doi:10.1016/j.jorganchem.2009.09.044

Cited by 7 publications

(7 citation statements)

References 32 publications

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“…For benzenesulfonates a highly polarized S + −O − bond was assumed . The decreased infrared stretching frequencies of the S=O bond, ν S=O , in phenyl tosylates (ν asym = 1385 cm ‐1 for the SO 2 group in 4‐CH 3 ‐C 6 H 4 SO 2 OC 6 H 5 (Table ), ν asym = 1384 cm ‐1 for C 6 H 4 SO 2 OC 6 H 5 ) with respect to that of the carbonyl C=O bond in phenyl benzoates ( ν CO = 1742.6 cm ‐1 for C 6 H 5 CO 2 C 6 H 5 ) also demonstrate the increased ionic bond character of the sulfonyl SO 2 group in phenyl tosylates as compared to that of the carbonyl C=O in phenyl benzoates. The δ ( 17 O) values of the single‐bonded bridged oxygen in OPh for phenyl tosylates series (between 174.9 and 196.1 ppm, Table ) appeared to lie nearly in the same range as δ ( 17 O) values for substituted phenyl benzoates ( δ ( 17 O) values between 170–190 ppm).…”

Section: Resultsmentioning

confidence: 99%

¹⁷O NMR studies of ortho‐substituent effects in substituted phenyl tosylates

Nummert

Mäemets

Piirsalu

et al. 2012

Magnetic Reson in Chemistry

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(17)O NMR spectra for 35 ortho-, para-, and meta-substituted phenyl tosylates (phenyl 4-methylbenzenesulfonates), 4-CH(3)-C(6)H(4) SO(2)OC(6)H(4)-X, at natural abundance in acetonitrile at 50 °C were recorded. The (17)O NMR chemical shifts, δ((17)O), of the sulfonyl (SO(2)) and the single-bonded phenoxy (OPh) oxygens for para and meta derivatives correlated well with dual substituent parameter treatment using the Taft inductive, σ(I), and resonance, σº(R), constants. The influence of ortho substituents on the sulfonyl oxygen and the single-bonded phenoxy oxygen chemical shifts, δ((17)O), was found to be nicely described by the Charton equation: δ((17)O)(ortho) = δ((17)O)(H) + ρ(I)σ(I) + ρ(R)σ°(R) + δE(s)(B) when the data treatment was performed separately for electron-donating +R substituents and electron-attracting -R substituents. Electron-attracting meta and para substituents in the phenyl moiety caused deshielding while the electron-donating meta, para and ortho +R substituents produce shielding effects on the sulfonyl (SO(2)) and single-bonded phenoxy (OPh) oxygens. The influence of ortho inductive and resonance effects in the case of +R substituents was found to be approximately twice higher than the corresponding influence from the para position. Due to the steric effect of ortho substituents a decrease in shielding of the oxygens at the sulfonyl group (δE(s)(B) > 0, E(s)(B) < 0) was detected.

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Section: Resultsmentioning

confidence: 99%

¹⁷O NMR studies of ortho‐substituent effects in substituted phenyl tosylates

Nummert

Mäemets

Piirsalu

et al. 2012

Magnetic Reson in Chemistry

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“…Then, a simple rate law can be derived for the sulfonate addition of Grignard reagents in THF:toluene comprising fast equilibrium formation of complex A [44] and rate determining second order [34][35][36] conversion of A to the product intermediate B;…”

Section: ð1þmentioning

confidence: 99%

“…However, the kinetic and mechanistic details of C-S coupling of aryl Grignard reagents with aryl arenesulfonates have been recently reported by Erdik et al [34][35][36]. A stepwise S N a mechanism was offered (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

An insight into the C–S coupling mechanism of aryl Grignard reagents with aryl arenesulfonates

Eroğlu

2011

Reac Kinet Mech Cat

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The reaction rate and thermodynamic parameters in the reaction of phenylmagnesium bromide with phenyl tosylate in THF:toluene binary solvents and also in toluene were analyzed. The relative changes in the rate constants are strictly bound to changes in the equilibrium constant of complex formation between the sulfonate and the Grignard reagent by replacement of a donor THF molecule as well as the transfer rate of the carbanion to the sulfonate in the complex. These results provide another support for asynchronous S N a mechanism comprising a four-center transition state mechanism.

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“…Proton shifts in related intermolecular complexes, formed between pyridines and 18 O-dichloroacetic acid, have been studied with low-temperature 13 C NMR (Scheme 3). 6 The perturbation of the 18 O-induced 13 C-chemical shifts, at temperatures of 230 K and 192 K, was used to distinguish a shared H-bond, with a single-well potential, from a pair of tautomers (a double-well potential). In the CD 2 Cl 2 solvent, there was a maximum in the 18 O-induced shift of the 13 C signal with matched H-bond donors.…”

mentioning

confidence: 99%

“…6 The perturbation of the 18 O-induced 13 C-chemical shifts, at temperatures of 230 K and 192 K, was used to distinguish a shared H-bond, with a single-well potential, from a pair of tautomers (a double-well potential). In the CD 2 Cl 2 solvent, there was a maximum in the 18 O-induced shift of the 13 C signal with matched H-bond donors. This indicates the presence of tautomers, because the enhancement of the shift is caused by the additional perturbation of isotopic substitution on the tautomeric equilibrium.…”

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confidence: 99%

Reaction mechanisms: polar reactions

Croft¹,

Davies²

2011

Annu. Rep. Prog. Chem., Sect. B: Org. Chem.

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This review presents highlights from papers published in 2010 reporting the mechanistic studies of polar reactions across a diverse range of fields, and is primarily focussed on experimental investigations. A number of examples related to biological systems are included, where the reaction mechanisms are often both complicated and enhanced by supramolecular factors. The breadth of modern physical organic chemistry means that the subheadings used throughout the review should be used as guidelines, as for many studies it is possible to categorise them in a number of different ways. Hydrogen transferThe transfer of hydrogen, whether as a proton or as hydride, is an important step in many different processes. As such, this section covers a range of reactions where hydrogen plays a central role.Natural processes are a rich source of hydrogen transfer reactions, and, in particular, the ability of protons and hydride anions to be transferred with extremely large kinetic isotope effects (KIEs) through tunnelling remains intriguing. The effect of distance between the donor and acceptor for hydride transfer on force constants in enzymecatalysed reactions has been examined for the enzyme morphinone reductase (Scheme 1). 1 Scheme 1 Hydride transfer from NADH to FMN in morphinone reductase.

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Sulfonyl transfer mechanism in C–S coupling of phenylmagnesium bromide with phenyl arenesulfonates

Cited by 7 publications

References 32 publications

¹⁷O NMR studies of ortho‐substituent effects in substituted phenyl tosylates

¹⁷O NMR studies of ortho‐substituent effects in substituted phenyl tosylates

An insight into the C–S coupling mechanism of aryl Grignard reagents with aryl arenesulfonates

Reaction mechanisms: polar reactions

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Sulfonyl transfer mechanism in C–S coupling of phenylmagnesium bromide with phenyl arenesulfonates

Cited by 7 publications

References 32 publications

17O NMR studies of ortho‐substituent effects in substituted phenyl tosylates

17O NMR studies of ortho‐substituent effects in substituted phenyl tosylates

An insight into the C–S coupling mechanism of aryl Grignard reagents with aryl arenesulfonates

Reaction mechanisms: polar reactions

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¹⁷O NMR studies of ortho‐substituent effects in substituted phenyl tosylates

¹⁷O NMR studies of ortho‐substituent effects in substituted phenyl tosylates