1997
DOI: 10.1039/a703372i
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Substituent effect on the allyl vinyl sulfide rearrangement (thio-Claisen rearrangement) and the vinylthioethanimine rearrangement. A theoretical study

Abstract: The transition structures for the [3,3] sigmatropic rearrangements of a variety of substituted allyl vinyl sulfides (X᎐ ᎐ CH) and vinylthioethanimines (X᎐ ᎐ N) H 2 C᎐ ᎐ CR᎐S᎐CH 2 ᎐CRЈ᎐ ᎐ XRЉ (R = NH 2 ; RЈ = BH 2 , CN; RЉ = CF 3 ) have been located using ab initio and DFT (B3LYP) calculations and the 6-31G* basis set. Relative energies have been estimated using post-HF calculations up to the QCISD(T)/6-31G*//B3LYP/ 6-31G* level. Solvent effects on these processes have been simulated by means of SCRF computatio… Show more

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Cited by 6 publications
(5 citation statements)
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“…Furthermore, solvation effects appear to have considerable impact on the activation barrier: depending on their dielectric constant polar solvents lead to an increase of the barriers by several kcal mol À1 for the protonated species, while lowering the activation barrier of the neutral compound. This result is in agreement with the studies of Hillier et al [70] and others [71,72] on the solvent dependence of the Claisen rearrangement. The low activation energies of the protonated forms relative to their neutral counterparts arises mainly from the higher charge delocalization in the transition state of the former.…”
Section: Resultssupporting
confidence: 93%
“…Furthermore, solvation effects appear to have considerable impact on the activation barrier: depending on their dielectric constant polar solvents lead to an increase of the barriers by several kcal mol À1 for the protonated species, while lowering the activation barrier of the neutral compound. This result is in agreement with the studies of Hillier et al [70] and others [71,72] on the solvent dependence of the Claisen rearrangement. The low activation energies of the protonated forms relative to their neutral counterparts arises mainly from the higher charge delocalization in the transition state of the former.…”
Section: Resultssupporting
confidence: 93%
“…15 Among the activation barriers calculated for the Claisen rearrangement with various methods, the MP4 and B3LYP/6-31G* calculations have shown the best agreement with experimental values. 16-18 B3LYP/6-31G* has also been used to model transition structures for a variety of allyl vinyl sulfides and vinylthioethanimines 13 as well as hetero-Cope type rearrangement reactions. 18 We have used the B3LYP/6-31G* method throughout this study because of its excellent compromise between accuracy and computer time.…”
Section: Methodsmentioning
confidence: 99%
“…The transition structures for the [3,3] sigmatropic rearrangements of a variety of substituted allyl vinyl sulfides and vinylthioethanimines have been located using ab initio and B3LYP calculations. 13 The results showed that combined donoracceptor disubstitutions considerably increase the reactivity of the allyl vinyl sulfide. Thus, 2-amino-5-cyano disubstitution lowers the enthalpy of activation by 6.6 kcal/mol and increases the exothermicity of the rearrangement by 13.0 kcal/mol at the MP4SDTQ/6-31G*//B3LYP/6-31G* level.…”
Section: Experimental Substituent Effectmentioning
confidence: 99%
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“…The applicability of this methodology is low because of the instability of the product (thioaldehyde). 13,14 This subject prompted the development of qualifications to snaring and transforming the unstable product into a more stable compound, for example, the hydrolysis of the thioaldehyde into the corresponding aldehyde. 15 In this study, we calculated and compared kinetic and thermodynamic quantities for the Claisen rearrangement of 3-(vinyloxy)prop-1-ene and the thio-Claisen rearrangement of allyl vinyl sulfide in the gas phase.…”
Section: Introductionmentioning
confidence: 99%