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Volumn 72, Issue 12, 2007, Pages 4351-4357

A highly selective rearrangement of a housane-derived cation radical: An electrochemically mediated transformation

Author keywords

[No Author keywords available]

Indexed keywords

CYCLIC VOLTAMMOGRAM; CYCLOPENTADIENES; ELECTROSTATIC POTENTIAL; HYDROGEN SHIFTS;

EID: 34250184636     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo070190x     Document Type: Article
Times cited : (34)

References (38)
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    • For a review concerning the interaction of silicon with positively charged carbon at the α, β, γ, and δ positions, see
    • (a) For a review concerning the interaction of silicon with positively charged carbon at the α, β, γ, and δ positions, see: Lambert, J. B. Tetrahedron 1990, 46, 2677-2689.
    • (1990) Tetrahedron , vol.46 , pp. 2677-2689
    • Lambert, J.B.1
  • 4
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    • reports a novel silicon γ-aryl effect upon redox potential
    • (b) Kaimakliotis, C; Fry, A. J. J. Org. Chem. 2003, 68, 9893-9898; reports a novel silicon γ-aryl effect upon redox potential.
    • (2003) J. Org. Chem , vol.68 , pp. 9893-9898
    • Kaimakliotis, C.1    Fry, A.J.2
  • 5
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    • See, for example, the structures shown in
    • See, for example, the structures shown in: Wilson, R. M.; Danishefsky, S. J. Acc. Chem. Res. 2006, 39, 539-549.
    • (2006) Acc. Chem. Res , vol.39 , pp. 539-549
    • Wilson, R.M.1    Danishefsky, S.J.2
  • 6
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    • For example, see: a
    • For example, see: (a) Cossy, J.; Belotti, D. Tetrahedron 2006, 62, 6459-6470;
    • (2006) Tetrahedron , vol.62 , pp. 6459-6470
    • Cossy, J.1    Belotti, D.2
  • 7
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    • Floreancig, P. E. Tetrahedron 2006, 62, 6447-6594 (Symposium-in-Print Number 121).
    • Floreancig, P. E. Tetrahedron 2006, 62, 6447-6594 (Symposium-in-Print Number 121).
  • 9
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    • Moss, R. A, Platz, M. S, Jones, M, Jr, Eds, John Wiley & Sons: New York, Chapter 6, pp
    • (c) Roth, H. D. In Reactive Intermediate Chemistry; Moss, R. A., Platz, M. S., Jones, M., Jr., Eds.; John Wiley & Sons: New York, 2004; Chapter 6, pp 205-272.
    • (2004) Reactive Intermediate Chemistry , pp. 205-272
    • Roth, H.D.1
  • 23
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    • All calculations performed at UCSB used the SPARTAN '04 Macintosh software package, while those performed at UCD used the GAUSSIAN03 suite of programs (Frisch, M. J.; et al. Gaussian 03; Gaussian, Inc.: Wallingford, CT, 2003).
    • (a) All calculations performed at UCSB used the SPARTAN '04 Macintosh software package, while those performed at UCD used the GAUSSIAN03 suite of programs (Frisch, M. J.; et al. Gaussian 03; Gaussian, Inc.: Wallingford, CT, 2003).
  • 24
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    • Geometries and HOMO energies for the systems illustrated in Table 1 were calculated at the HF/3-21G(d), HF/6-31G(d), and B3LYP/6-31G(d) levels of theory. The trends in HOMO energies vary slightly with different levels of theory, but in a manner that does not change any of our conclusions. See Supporting Information for additional details on all of these calculations, including pictures of the computed HOMOs.
    • (b) Geometries and HOMO energies for the systems illustrated in Table 1 were calculated at the HF/3-21G(d), HF/6-31G(d), and B3LYP/6-31G(d) levels of theory. The trends in HOMO energies vary slightly with different levels of theory, but in a manner that does not change any of our conclusions. See Supporting Information for additional details on all of these calculations, including pictures of the computed HOMOs.
  • 27
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    • Electrogenerated Reagents
    • 4th ed, Lund, H, Hammerich, O, Eds, Marcel Dekker: New York, Chapter 29
    • (b) Simonet, J.; Pilard, J.-F. Electrogenerated Reagents. In Organic Electrochemistry, 4th ed.; Lund, H., Hammerich, O., Eds.; Marcel Dekker: New York, 2001; Chapter 29.
    • (2001) Organic Electrochemistry
    • Simonet, J.1    Pilard, J.-F.2
  • 29
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    • The use of 20 mol, of the mediator leads to a significant rate increase, thereby allowing the complete consumption of the starting material in 2 h or less
    • The use of 20 mol % of the mediator leads to a significant rate increase, thereby allowing the complete consumption of the starting material in 2 h or less.
  • 30
    • 34250196249 scopus 로고    scopus 로고
    • Interestingly, GCMS analysis shows that heating 18 to 300°C for 20 min affords both regioisomers. In the thermal process, the major product corresponds to the isomer that is not observed electrochemically.
    • Interestingly, GCMS analysis shows that heating 18 to 300°C for 20 min affords both regioisomers. In the thermal process, the major product corresponds to the isomer that is not observed electrochemically.
  • 31
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    • Geometries for structures involved in the rearrangement were optimized using the B3LYP/6-31G(d) method Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652;
    • Geometries for structures involved in the rearrangement were optimized using the B3LYP/6-31G(d) method (Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652;
  • 34
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    • on a model system with the benzyl group replaced by a methyl group
    • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623-11627) on a model system with the benzyl group replaced by a methyl group.
    • (1994) J. Phys. Chem , vol.98 , pp. 11623-11627
    • Stephens, P.J.1    Devlin, F.J.2    Chabalowski, C.F.3    Frisch, M.J.4
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    • All structures were characterized by frequency calculations. Intrinsic reaction coordinate (IRC) calculations Gonzalez, C.; Schlegel, H. B. J. Phys. Chem. 1990, 94, 5523-5527;
    • All structures were characterized by frequency calculations. Intrinsic reaction coordinate (IRC) calculations (Gonzalez, C.; Schlegel, H. B. J. Phys. Chem. 1990, 94, 5523-5527;
  • 36
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    • Fukui, K. Acc. Chem. Res. 1981, 14, 363-368 were also used to characterize transition structures. Note that, as a test of this methodology, we attempted to predict the major product without prior knowledge of the experimental result; in this case, the prediction proved to be correct.
    • Fukui, K. Acc. Chem. Res. 1981, 14, 363-368) were also used to characterize transition structures. Note that, as a test of this methodology, we attempted to predict the major product without prior knowledge of the experimental result; in this case, the prediction proved to be correct.
  • 37
    • 36549094556 scopus 로고    scopus 로고
    • CCSD/6-31G(d) (Scuseria, G. E.; Schaefer, H. F., III. J. Chem. Phys. 1989, 90, 3700-3703) single point calculations were also performed. See Supporting Information for additional details.
    • CCSD/6-31G(d) (Scuseria, G. E.; Schaefer, H. F., III. J. Chem. Phys. 1989, 90, 3700-3703) single point calculations were also performed. See Supporting Information for additional details.
  • 38
    • 34250202339 scopus 로고    scopus 로고
    • Stabilization of an incipient or fully formed cation (or radical) could also be achieved through participation by the ether oxygen. We have no evidence to favor or disfavor this possibility
    • Stabilization of an incipient or fully formed cation (or radical) could also be achieved through participation by the ether oxygen. We have no evidence to favor or disfavor this possibility.


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