The thio-Wittig rearrangement of deprotonated allyl methyl sulfide. A gas-phase unimolecular isomerization probed with a variable temperature flowing afterglow-triple quadrupole device

Journal of the American Chemical Society

Volumn 118, Issue 6, 1996, Pages 1398-1407

  Ahmad, Mohammad R ^a   Dahlke, Gregg D ^a   Kass, Steven R ^a  

^a University of Minnesota   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACROLEIN; ACROLEIN DERIVATIVE; THIOL DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; TEMPERATURE; THERMODYNAMICS;

EID: 0029884995     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja953116h     Document Type: Article

References (118)

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85. - (m/z 107, 60%).
86. It is possible to convert all of the m/z 87 ion to m/z 90 with this reagent.
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88. All acidities and other tbermodynamic data, unless otherwise noted, come from: Lias, S. G.; Bartmess, J. E.; Liebman, J. F., Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phy. Chem. Ref. Data 1988, 17. Supplement 1 or the slightly updated form available on a personal computer, NIST Negative Ion Energetics Database (Version 3.00. 1993); NIST Standard Reference Database 19B.
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94. 3 with hydroxide results in a M-H:M-D ratio which seems to be somewhat dependent on the temperature.
95. The radical anion of thioacrolein presumably undergoes some electron detachment at elevated temperatures. It never amounts to more than approximately 25% of 1a.
96. -1), however, appears to be significantly too low.
97. For calculations on the thiomethyl anion, see: Downard, K. M.; Sheldon, J. C.; Bowie, J. H.; Lewis, D. E.; Hayes, R. N. J. Am. Chem. Soc. 1989, 111, 8112.
98. In our calculations on 1a, 3a, and 4a the methyl group was replaced by a hydrogen atom. This substitution should have little impact on the computed results.
99. -1 were ascribed to the heats of formation of 1 and 3 and were derived using the following reference: Benson, S. W. Thermochemical Kinetics. 2nd ed.; John Wiley and Sons: New York, 1976.
100. The cited energies are based on QCISD(T)/6-311++G(d.p)//HF/ 6-31+G(d) calculations. For further details and the effect of correlation on the energies, see the supporting information.
101. The sulfur 3p orbitals are higher in energy than oxygen's 2p orbitals so the interaction with the olefinic π bond in the thioenolate is less.
102. -1.
103. -1) and the reaction distance (100 cm).
104. Houk, K. N.; Li, Y.; Evanseck, J. D. Angew. Chem., Int. Ed. Engl. 1992, 31, 682.
105. An alternative elimination-addition mechanism cannot be excluded, but we think this pathway is less likely based upon thermodynamic grounds. See the text for additional details.
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108. 3,*) = 35.1. These energies come from or can be derived from data in refs 29, 46, and Nobes, R. H.; Radom, L. Chem. Phys. Lett. 1992, 189, 554.
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111. Fleming, I. Frontier Orbitals and Organic Chemical Reactions; John Wiley and Sons: New York, 1976.
112. 2CH) is employed, however, very different activation parameters (bigger enthalpies and much less negative entropies) are obtained, and a CIDNP signal can be detected. In these cases, a stepwise mechanism seems to be operative. For further details, see ref 7c.
113. Woodward, R. B.; Hoffmann, R. The Conservation of Orbital Symmetry; Academic Press: Germany, 1971.
114. -1 (MP3/6-311++G-(d.p)//6-31G(d)) barrier for rotation about allyl anion. Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61.
115. Thioacrolein, undoubtedly, has a larger dipole moment and is considerably more polarizable than methyl radical so the interaction energy in IV is larger than in III. (56) For details regarding natural atomic populations, see: Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735.
116. It is interesting to note that in both the sulfur and oxygen cases the interaction of methyl radical with the second highest π-type orbital leads to the correct prediction. For example, the SOMO-2 of thioacrolein radical anion (cis or trans) has a much larger coefficient at C3 than C1. Moreover, the energy match between this MO and the SOMO of methyl radical is much better than between the two SOMOs.
117. -) = -32.7. These energies come from refs 28, 39, 47, and 48.
118. -1, respectively) are also larger, and this too explains their stability. Note, this energetic data was obtained using refs 28 and 48.