Stereochemistry of allylic rearrangements. XVI. Stereochemistry of ion-pair return in the trans-.alpha.,.gamma.-methylphenylallyl p-nitrobenzoate system

Goering, Harlan L.; Koermer, Gerald S.; Linsay, Ernest C.

doi:10.1021/ja00734a034

Cited by 16 publications

(5 citation statements)

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“…were determined as described earlier. 5 In these experiments the I- OPNB concentration varied from 0.06 to 0.12 M and in all cases 50% excess 2,6-lutidine was present. The change in rotation was at least 0.7°and individual readings were obtained with a precision of ±0.002°.…”

Section: Methodsmentioning

confidence: 85%

Ion-pair return associated with solvolysis of oxygen-18-labeled 1,2-dimethyl-exo-2-norbornyl p-nitrobenzoate

Goering¹,

Humski²

1975

J. Org. Chem.

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24) Another nitrogen-centered free radical that reacts with benzene is the W-succinimidyl radical;25 Hedaya et al. showed that this radical most probably has a -type electronic ground state.163 (25) D. R. Howton, J. Am. Chem. Soc., 69, 2060 (1947. ( 26) When a frozen solution of 5a in methylcyclohexane (77 K) was irradiated in the cavity of an ESR apparatus, only signals of methyl radicals and (probably) f-BuOO • radicals were observed. (27) B.

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Section: Methodsmentioning

confidence: 85%

Ion-pair return associated with solvolysis of oxygen-18-labeled 1,2-dimethyl-exo-2-norbornyl p-nitrobenzoate

Goering¹,

Humski²

1975

J. Org. Chem.

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“…For background to the stereochemistry of allylic rearrangements, see: Hughes (1941); Raber et al (1974); Goering et al (1971). For details of the synthesis, see: Troshin et al (2011); Gao et al (1987); Roos & Donovan (1996).…”

Section: Related Literaturementioning

confidence: 99%

“…Allylic substances have been used since 1940s to get an insight into the detailed mechanism of S N 1 reactions due to the possibility of allylic rearrangement which gives additional analytical probe not available for other systems [Hughes (1941); Raber et al (1974)]. Pioneering research of Goering et al (1971) on the solvolyses of optically active allyl derivatives provided lots of information about ion-pairing in S N 1 solvolyses (Goering et al, 1971), however, due to the lack of analytical methods available during Goering's time, many questions about ion pair dynamics and stereochemistry of allylic rearrangements remained open. As modern analytical techniques such as chiral HPLC and laser-flash photolysis give unprecedented insights in the reaction kinetics, we decided to reconsider the problem of stereochemistry of allylic rearrangements.…”

Section: S1 Commentmentioning

confidence: 99%

(R,E)-3-(4-Chlorophenyl)-1-phenylallyl 4-nitrobenzoate

2012

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The title compound, C22H16ClNO4, adopts a conformation in which the phenyl ring plane forms similar dihedral angles with the nitrobenzoate C6 ring [76.97 (8)°] and the chlorophenyl group [76.95 (8)°]; the dihedral angle between the chlorophenyl and nitrobenzoate rings is 66.43 (8)°. In the crystal, π–π stacking is observed between the latter two planes, with a dihedral angle of 1.79 (8)° and a centroid–centroid distance of 3.735 (1) Å. In addition, molecules are linked along [100] by weak C—H...O contacts

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“…Because of the occurrence of allylic rearrangements, solvolyses of allyl derivatives were of particular importance for the development of the mechanistic understanding of aliphatic nucleophilic substitutions . Pioneering studies by Goering brought new insights into structure and reactivities of ion pairs; however, the mechanistic investigations were limited by the analytical methods available at that time. In a recent study, we employed the capability of modern HPLC to clarify the ion-pair dynamics during the solvolyses of unsymmetrical 1,3-diarylallyl derivatives and showed how eq can be used to predict the extent of external and internal return during solvolysis .…”

Section: Introductionmentioning

confidence: 99%

Electrofugalities of 1,3-Diarylallyl Cations

Troshin

Mayr

2013

J. Org. Chem.

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Heterolysis rate constants k1 of differently substituted 1,3-diarylallyl halides and carboxylates have been determined in various solvents. The linear free energy relationship log k1 = s(f)(N(f) + E(f)) was found to predict the heterolysis rates (log k1) of 1,3-diarylallyl derivatives with a standard deviation of 0.26, corresponding to a factor of 1.82 in k1, and maximum deviation in k1 of a factor of 5. Some systematic deviations are evident, however. Thus, 1,3-diarylallyl carboxylates always react faster and 1,3-diarylallyl chlorides always react more slowly than calculated by the quoted correlation equation when both types of leaving groups were used to determine the electrofugality parameters E(f). As 1,3-diarylalyl cations are generated faster in solvolysis reactions and also react faster with nucleophiles than benzhydrylium ions of similar thermodynamic stabilities, i.e., Lewis acidities, one can conclude that the reactions involving 1,3-diarylallyl cations proceed with lower intrinsic barriers than those involving benzhydrylium ions. The electrofugality parameters E(f) of 1,3-diarylallylium ions determined in this work were combined with the electrophilicity parameters E of the corresponding cations as well as with the results on ion pair dynamics reported in preceding papers for generating the full mechanistic spectrum of 1,3-diarylallyl solvolyses.

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Stereochemistry of allylic rearrangements. XVI. Stereochemistry of ion-pair return in the trans-.alpha.,.gamma.-methylphenylallyl p-nitrobenzoate system

Cited by 16 publications

References 1 publication

Ion-pair return associated with solvolysis of oxygen-18-labeled 1,2-dimethyl-exo-2-norbornyl p-nitrobenzoate

Ion-pair return associated with solvolysis of oxygen-18-labeled 1,2-dimethyl-exo-2-norbornyl p-nitrobenzoate

(R,E)-3-(4-Chlorophenyl)-1-phenylallyl 4-nitrobenzoate

Electrofugalities of 1,3-Diarylallyl Cations

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