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Volumn 42, Issue 47, 2003, Pages 5877-5882

Breaking Down Barriers: The Liaison between Sigmatropic Shifts, Electrocyclic Reactions, and Three-Center Cations

Author keywords

Carbocations; Electrocyclic reaction; Pericyclic reaction; Proton affinity; Sigmatropic rearrangement; Transition states

Indexed keywords

ELECTRONS; POSITIVE IONS;

EID: 0347419941     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200352853     Document Type: Article
Times cited : (20)

References (51)
  • 3
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    • For leading references on calculations and experiments on other related sigmatropic shifts, see: a) C. W. Spangler, Chem. Rev. 1976, 76, 187-217;
    • (1976) Chem. Rev. , vol.76 , pp. 187-217
    • Spangler, C.W.1
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    • reference [1a]
    • g) reference [1a].
  • 10
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    • Cationic three-center two-electron arrays have been studied extensively; for leading references, see: a) J. E. McMurry, T. Lectka, Acc. Chem. Res. 1992, 25, 47-53;
    • (1992) Acc. Chem. Res. , vol.25 , pp. 47-53
    • McMurry, J.E.1    Lectka, T.2
  • 14
    • 0000584447 scopus 로고
    • a) Other researchers have made similar analogies for neutral sigmatropic shifts. See, for example, K. N. Houk, Y. Li, J. D. Evanseck, Angew. Chem. 1992, 104, 711-739; Angew. Chem. Int. Ed. Engl. 1992, 31, 682-708; and F. Jensen, J. Am. Chem. Soc. 1995, 117, 7487-7492;
    • (1992) Angew. Chem. , vol.104 , pp. 711-739
    • Houk, K.N.1    Li, Y.2    Evanseck, J.D.3
  • 15
    • 33748960439 scopus 로고
    • a) Other researchers have made similar analogies for neutral sigmatropic shifts. See, for example, K. N. Houk, Y. Li, J. D. Evanseck, Angew. Chem. 1992, 104, 711-739; Angew. Chem. Int. Ed. Engl. 1992, 31, 682-708; and F. Jensen, J. Am. Chem. Soc. 1995, 117, 7487-7492;
    • (1992) Angew. Chem. Int. Ed. Engl. , vol.31 , pp. 682-708
  • 16
    • 0000243301 scopus 로고
    • a) Other researchers have made similar analogies for neutral sigmatropic shifts. See, for example, K. N. Houk, Y. Li, J. D. Evanseck, Angew. Chem. 1992, 104, 711-739; Angew. Chem. Int. Ed. Engl. 1992, 31, 682-708; and F. Jensen, J. Am. Chem. Soc. 1995, 117, 7487-7492;
    • (1995) J. Am. Chem. Soc. , vol.117 , pp. 7487-7492
    • Jensen, F.1
  • 17
    • 0001254713 scopus 로고
    • b) it has been proposed that the nature (protonic or hydridic) of the migrating hydrogen in sigmatropic shifts can vary considerably, depending on the nature of the hydrocarbon framework over which it migrates; see: S. D. Kahn, W. J. Hehre, N. G. Rondan, K. N. Houk, J. Am. Chem. Soc. 1985, 107, 8291-8292; see also: I. V. Alabugin, M. Manoharan, B. Breiner, F. D. Lewis, J. Am. Chem. Soc. 2003, 125, 9329-9342.
    • (1985) J. Am. Chem. Soc. , vol.107 , pp. 8291-8292
    • Kahn, S.D.1    Hehre, W.J.2    Rondan, N.G.3    Houk, K.N.4
  • 18
    • 0042208364 scopus 로고    scopus 로고
    • b) it has been proposed that the nature (protonic or hydridic) of the migrating hydrogen in sigmatropic shifts can vary considerably, depending on the nature of the hydrocarbon framework over which it migrates; see: S. D. Kahn, W. J. Hehre, N. G. Rondan, K. N. Houk, J. Am. Chem. Soc. 1985, 107, 8291-8292; see also: I. V. Alabugin, M. Manoharan, B. Breiner, F. D. Lewis, J. Am. Chem. Soc. 2003, 125, 9329-9342.
    • (2003) J. Am. Chem. Soc. , vol.125 , pp. 9329-9342
    • Alabugin, I.V.1    Manoharan, M.2    Breiner, B.3    Lewis, F.D.4
  • 19
    • 0035353517 scopus 로고    scopus 로고
    • For leading references, see: a) R. V. Williams, Chem. Rev. 2001, 101, 1185-1204;
    • (2001) Chem. Rev. , vol.101 , pp. 1185-1204
    • Williams, R.V.1
  • 23
    • 0000189651 scopus 로고
    • Geometries were optimized (without symmetry constraints) at the B3LYP/6-31G(d) level (A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377; C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789; P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11 623-11 627), whose effectiveness in describing structures and energetics for pericyclic reactions is well-documented (see, for example: O. Wiest, D. C. Montiel, K. N. Houk, J. Phys. Chem. A 1997,101, 8378-8388; K. N. Houk, B. R. Beno, M. Nendel, K. Black, H. Y. Yoo, S. Wilsey, J. K. Lee, J. Mol. Struct. 1997, 398-399, 169-179; D. A. Hrovat, B. R. Beno, H. Lange, H.-Y. Yoo, K. N. Houk, W. T. Borden, J. Am. Chem. Soc. 2000, 122, 7456-7460); all structures were characterized by frequency calculations at the B3LYP/6-31G(d) level, and zeropoint energy corrections (scaled by 0.9806 as recommended in A. P. Scott, L. Radom, J. Phys. Chem. 1996, 100, 16502-16513) from these calculations are included in the reported energies. Ball-and-stick drawings were produced with Ball & Stick (N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University Linz, 2000).
    • (1993) J. Chem. Phys. , vol.98 , pp. 5648-5652
    • Becke, A.D.1
  • 24
    • 34250817103 scopus 로고
    • Geometries were optimized (without symmetry constraints) at the B3LYP/6-31G(d) level (A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377; C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789; P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11 623-11 627), whose effectiveness in describing structures and energetics for pericyclic reactions is well-documented (see, for example: O. Wiest, D. C. Montiel, K. N. Houk, J. Phys. Chem. A 1997,101, 8378-8388; K. N. Houk, B. R. Beno, M. Nendel, K. Black, H. Y. Yoo, S. Wilsey, J. K. Lee, J. Mol. Struct. 1997, 398-399, 169-179; D. A. Hrovat, B. R. Beno, H. Lange, H.-Y. Yoo, K. N. Houk, W. T. Borden, J. Am. Chem. Soc. 2000, 122, 7456-7460); all structures were characterized by frequency calculations at the B3LYP/6-31G(d) level, and zeropoint energy corrections (scaled by 0.9806 as recommended in A. P. Scott, L. Radom, J. Phys. Chem. 1996, 100, 16502-16513) from these calculations are included in the reported energies. Ball-and-stick drawings were produced with Ball & Stick (N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University Linz, 2000).
    • (1993) J. Chem. Phys. , vol.98 , pp. 1372-1377
    • Becke, A.D.1
  • 25
    • 0345491105 scopus 로고
    • Geometries were optimized (without symmetry constraints) at the B3LYP/6-31G(d) level (A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377; C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789; P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11 623-11 627), whose effectiveness in describing structures and energetics for pericyclic reactions is well-documented (see, for example: O. Wiest, D. C. Montiel, K. N. Houk, J. Phys. Chem. A 1997,101, 8378-8388; K. N. Houk, B. R. Beno, M. Nendel, K. Black, H. Y. Yoo, S. Wilsey, J. K. Lee, J. Mol. Struct. 1997, 398-399, 169-179; D. A. Hrovat, B. R. Beno, H. Lange, H.-Y. Yoo, K. N. Houk, W. T. Borden, J. Am. Chem. Soc. 2000, 122, 7456-7460); all structures were characterized by frequency calculations at the B3LYP/6-31G(d) level, and zeropoint energy corrections (scaled by 0.9806 as recommended in A. P. Scott, L. Radom, J. Phys. Chem. 1996, 100, 16502-16513) from these calculations are included in the reported energies. Ball-and-stick drawings were produced with Ball & Stick (N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University Linz, 2000).
    • (1988) Phys. Rev. B , vol.37 , pp. 785-789
    • Lee, C.1    Yang, W.2    Parr, R.G.3
  • 26
    • 33751157732 scopus 로고
    • Geometries were optimized (without symmetry constraints) at the B3LYP/6-31G(d) level (A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377; C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789; P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11 623-11 627), whose effectiveness in describing structures and energetics for pericyclic reactions is well-documented (see, for example: O. Wiest, D. C. Montiel, K. N. Houk, J. Phys. Chem. A 1997,101, 8378-8388; K. N. Houk, B. R. Beno, M. Nendel, K. Black, H. Y. Yoo, S. Wilsey, J. K. Lee, J. Mol. Struct. 1997, 398-399, 169-179; D. A. Hrovat, B. R. Beno, H. Lange, H.-Y. Yoo, K. N. Houk, W. T. Borden, J. Am. Chem. Soc. 2000, 122, 7456-7460); all structures were characterized by frequency calculations at the B3LYP/6-31G(d) level, and zeropoint energy corrections (scaled by 0.9806 as recommended in A. P. Scott, L. Radom, J. Phys. Chem. 1996, 100, 16502-16513) from these calculations are included in the reported energies. Ball-and-stick drawings were produced with Ball & Stick (N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University Linz, 2000).
    • (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
  • 27
    • 0031556561 scopus 로고    scopus 로고
    • Geometries were optimized (without symmetry constraints) at the B3LYP/6-31G(d) level (A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377; C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789; P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11 623-11 627), whose effectiveness in describing structures and energetics for pericyclic reactions is well-documented (see, for example: O. Wiest, D. C. Montiel, K. N. Houk, J. Phys. Chem. A 1997,101, 8378-8388; K. N. Houk, B. R. Beno, M. Nendel, K. Black, H. Y. Yoo, S. Wilsey, J. K. Lee, J. Mol. Struct. 1997, 398-399, 169-179; D. A. Hrovat, B. R. Beno, H. Lange, H.-Y. Yoo, K. N. Houk, W. T. Borden, J. Am. Chem. Soc. 2000, 122, 7456-7460); all structures were characterized by frequency calculations at the B3LYP/6-31G(d) level, and zeropoint energy corrections (scaled by 0.9806 as recommended in A. P. Scott, L. Radom, J. Phys. Chem. 1996, 100, 16502-16513) from these calculations are included in the reported energies. Ball-and-stick drawings were produced with Ball & Stick (N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University Linz, 2000).
    • (1997) J. Phys. Chem. A , vol.101 , pp. 8378-8388
    • Wiest, O.1    Montiel, D.C.2    Houk, K.N.3
  • 28
    • 30244518651 scopus 로고    scopus 로고
    • Geometries were optimized (without symmetry constraints) at the B3LYP/6-31G(d) level (A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377; C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789; P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11 623-11 627), whose effectiveness in describing structures and energetics for pericyclic reactions is well-documented (see, for example: O. Wiest, D. C. Montiel, K. N. Houk, J. Phys. Chem. A 1997,101, 8378-8388; K. N. Houk, B. R. Beno, M. Nendel, K. Black, H. Y. Yoo, S. Wilsey, J. K. Lee, J. Mol. Struct. 1997, 398-399, 169-179; D. A. Hrovat, B. R. Beno, H. Lange, H.-Y. Yoo, K. N. Houk, W. T. Borden, J. Am. Chem. Soc. 2000, 122, 7456-7460); all structures were characterized by frequency calculations at the B3LYP/6-31G(d) level, and zeropoint energy corrections (scaled by 0.9806 as recommended in A. P. Scott, L. Radom, J. Phys. Chem. 1996, 100, 16502-16513) from these calculations are included in the reported energies. Ball-and-stick drawings were produced with Ball & Stick (N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University Linz, 2000).
    • (1997) J. Mol. Struct. , vol.398-399 , pp. 169-179
    • Houk, K.N.1    Beno, B.R.2    Nendel, M.3    Black, K.4    Yoo, H.Y.5    Wilsey, S.6    Lee, J.K.7
  • 29
    • 0034625899 scopus 로고    scopus 로고
    • Geometries were optimized (without symmetry constraints) at the B3LYP/6-31G(d) level (A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377; C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789; P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11 623-11 627), whose effectiveness in describing structures and energetics for pericyclic reactions is well-documented (see, for example: O. Wiest, D. C. Montiel, K. N. Houk, J. Phys. Chem. A 1997,101, 8378-8388; K. N. Houk, B. R. Beno, M. Nendel, K. Black, H. Y. Yoo, S. Wilsey, J. K. Lee, J. Mol. Struct. 1997, 398-399, 169-179; D. A. Hrovat, B. R. Beno, H. Lange, H.-Y. Yoo, K. N. Houk, W. T. Borden, J. Am. Chem. Soc. 2000, 122, 7456-7460); all structures were characterized by frequency calculations at the B3LYP/6-31G(d) level, and zeropoint energy corrections (scaled by 0.9806 as recommended in A. P. Scott, L. Radom, J. Phys. Chem. 1996, 100, 16502-16513) from these calculations are included in the reported energies. Ball-and-stick drawings were produced with Ball & Stick (N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University Linz, 2000).
    • (2000) J. Am. Chem. Soc. , vol.122 , pp. 7456-7460
    • Hrovat, D.A.1    Beno, B.R.2    Lange, H.3    Yoo, H.-Y.4    Houk, K.N.5    Borden, W.T.6
  • 30
    • 0011083273 scopus 로고    scopus 로고
    • Geometries were optimized (without symmetry constraints) at the B3LYP/6-31G(d) level (A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377; C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789; P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11 623-11 627), whose effectiveness in describing structures and energetics for pericyclic reactions is well-documented (see, for example: O. Wiest, D. C. Montiel, K. N. Houk, J. Phys. Chem. A 1997,101, 8378-8388; K. N. Houk, B. R. Beno, M. Nendel, K. Black, H. Y. Yoo, S. Wilsey, J. K. Lee, J. Mol. Struct. 1997, 398-399, 169-179; D. A. Hrovat, B. R. Beno, H. Lange, H.-Y. Yoo, K. N. Houk, W. T. Borden, J. Am. Chem. Soc. 2000, 122, 7456-7460); all structures were characterized by frequency calculations at the B3LYP/6-31G(d) level, and zeropoint energy corrections (scaled by 0.9806 as recommended in A. P. Scott, L. Radom, J. Phys. Chem. 1996, 100, 16502-16513) from these calculations are included in the reported energies. Ball-and-stick drawings were produced with Ball & Stick (N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University Linz, 2000).
    • (1996) J. Phys. Chem. , vol.100 , pp. 16502-16513
    • Scott, A.P.1    Radom, L.2
  • 31
    • 18844424379 scopus 로고    scopus 로고
    • molecular graphics application for MacOS computers, Johannes Kepler University Linz
    • Geometries were optimized (without symmetry constraints) at the B3LYP/6-31G(d) level (A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377; C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789; P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11 623-11 627), whose effectiveness in describing structures and energetics for pericyclic reactions is well-documented (see, for example: O. Wiest, D. C. Montiel, K. N. Houk, J. Phys. Chem. A 1997,101, 8378-8388; K. N. Houk, B. R. Beno, M. Nendel, K. Black, H. Y. Yoo, S. Wilsey, J. K. Lee, J. Mol. Struct. 1997, 398-399, 169-179; D. A. Hrovat, B. R. Beno, H. Lange, H.-Y. Yoo, K. N. Houk, W. T. Borden, J. Am. Chem. Soc. 2000, 122, 7456-7460); all structures were characterized by frequency calculations at the B3LYP/6-31G(d) level, and zeropoint energy corrections (scaled by 0.9806 as recommended in A. P. Scott, L. Radom, J. Phys. Chem. 1996, 100, 16502-16513) from these calculations are included in the reported energies. Ball-and-stick drawings were produced with Ball & Stick (N. Müller, A. Falk, Ball & Stick V.3.7.6, molecular graphics application for MacOS computers, Johannes Kepler University Linz, 2000).
    • (2000) Ball & Stick V.3.7.6
    • Müller, N.1    Falk, A.2
  • 32
    • 0347611139 scopus 로고    scopus 로고
    • note
    • -1 in terms of electronic energies, and disappears when zero-point energy corrections are included.
  • 33
    • 0033612359 scopus 로고    scopus 로고
    • For a discussion of a different sort of connection between the properties of sigmatropic and electrocyclic transition structures (specifically in transition structures for certain rearrangments of α-lactams), see: D. J. Tantillo, K. N. Houk, R. V. Hoffman, J. Tao, J. Org. Chem. 1999, 64, 3830-3837.
    • (1999) J. Org. Chem. , vol.64 , pp. 3830-3837
    • Tantillo, D.J.1    Houk, K.N.2    Hoffman, R.V.3    Tao, J.4
  • 34
    • 0347611141 scopus 로고    scopus 로고
    • note
    • Only anionic and neutral electrocyclic transition structures and neutral and cationic sigmatropic transition structures are shown, since protonation of cationic electrocyclic transition structures would lead to dicationic sigmatropic transition structures and deprotonation of anionic sigmatropic transition structures would lead to dianionic electrocyclic transition structures.
  • 35
    • 0347611140 scopus 로고    scopus 로고
    • note
    • [4a]
  • 36
    • 0011190497 scopus 로고    scopus 로고
    • Calculated nucleus-independent chemical-shift (NICS) values (GIAO-B3LYP/6-31G(d); for details on the NICS method, see: P. von R. Schleyer, C. Maerker, A. Dransfeld, H. J. Jiao, N. J. R. von E. Hommes, J. Am. Chem. Soc. 1996, 118, 6317-6318; P. von R. Schleyer, M. Manoharan, Z.-X. Wang, B. Kiran, H. Jiao, R. Puchta, N. J. R. von E. Hommes, Org. Lett. 2001, 3, 2465-2468) for all of these transition structures are negative (ranging from - 13.6 to-7.2). For small systems, there is no clear connection between the NICS calculated for the electrocyclic and sigmatropic transition structures, but for larger systems, nearly identical NICS values were calculated for the electrocyclic and corresponding sigmatropic transition structures (-11.0 for the anionic 8π electrocyclic transition structure and -11.1 for the neutral [1,7] transition structure, and -9.6 for the neutral 8π electrocyclic transition structure and -9.9 for the cationic [1,8] transition structure). This reflects comparable degrees of delocalization in these structures, consistent with the similarities of their geometries. Deviations in the smaller systems may be due to differences in ring size for the electrocyclic and sigmatropic transition structures affecting the proximity of the points at which NICS values were calculated to the carbon-carbon bonds; such problems should be minimized in the larger systems.
    • (1996) J. Am. Chem. Soc. , vol.118 , pp. 6317-6318
    • Von R. Schleyer, P.1    Maerker, C.2    Dransfeld, A.3    Jiao, H.J.4    Von E. Hommes, N.J.R.5
  • 37
    • 0042888578 scopus 로고    scopus 로고
    • Calculated nucleus-independent chemical-shift (NICS) values (GIAO-B3LYP/6-31G(d); for details on the NICS method, see: P. von R. Schleyer, C. Maerker, A. Dransfeld, H. J. Jiao, N. J. R. von E. Hommes, J. Am. Chem. Soc. 1996, 118, 6317-6318; P. von R. Schleyer, M. Manoharan, Z.-X. Wang, B. Kiran, H. Jiao, R. Puchta, N. J. R. von E. Hommes, Org. Lett. 2001, 3, 2465-2468) for all of these transition structures are negative (ranging from - 13.6 to-7.2). For small systems, there is no clear connection between the NICS calculated for the electrocyclic and sigmatropic transition structures, but for larger systems, nearly identical NICS values were calculated for the electrocyclic and corresponding sigmatropic transition structures (-11.0 for the anionic 8π electrocyclic transition structure and -11.1 for the neutral [1,7] transition structure, and -9.6 for the neutral 8π electrocyclic transition structure and -9.9 for the cationic [1,8] transition structure). This reflects comparable degrees of delocalization in these structures, consistent with the similarities of their geometries. Deviations in the smaller systems may be due to differences in ring size for the electrocyclic and sigmatropic transition structures affecting the proximity of the points at which NICS values were calculated to the carbon-carbon bonds; such problems should be minimized in the larger systems.
    • (2001) Org. Lett. , vol.3 , pp. 2465-2468
    • Von R. Schleyer, P.1    Manoharan, M.2    Wang, Z.-X.3    Kiran, B.4    Jiao, H.5    Puchta, R.6    Von E. Hommes, N.J.R.7
  • 38
    • 0346350352 scopus 로고    scopus 로고
    • note
    • + model system, a bent structure with a C⋯C distance of 2.1 Å is preferred.
  • 39
    • 0001890453 scopus 로고
    • "Transition-state acidity" has been discussed previously; for leading references, see: J. L. Kurz, Acc. Chem. Res. 1972, 5, 1-9 and A. B. Watts, H. Patel, J. Theor. Biol. 2001, 209, 417-429. This concept does deal with the differences in rate for reactions involving protonated and unprotonated transition states, but is often (although not always) cast in terms of the protonation state of a catalytic molecule, rather than that of a transition structure itself. To our knowledge, this concept has not previously been applied to the analysis of pericyclic reactions.
    • (1972) Acc. Chem. Res. , vol.5 , pp. 1-9
    • Kurz, J.L.1
  • 40
    • 0035925933 scopus 로고    scopus 로고
    • "Transition-state acidity" has been discussed previously; for leading references, see: J. L. Kurz, Acc. Chem. Res. 1972, 5, 1-9 and A. B. Watts, H. Patel, J. Theor. Biol. 2001, 209, 417-429. This concept does deal with the differences in rate for reactions involving protonated and unprotonated transition states, but is often (although not always) cast in terms of the protonation state of a catalytic molecule, rather than that of a transition structure itself. To our knowledge, this concept has not previously been applied to the analysis of pericyclic reactions.
    • (2001) J. Theor. Biol. , vol.209 , pp. 417-429
    • Watts, A.B.1    Patel, H.2
  • 42
    • 0347611137 scopus 로고    scopus 로고
    • b) http://webbook.nist.gov/chemistry/;
  • 43
    • 0346980211 scopus 로고    scopus 로고
    • note
    • c) based on B3LYP6-31G(d) calculations on the reactants for the reactions corresponding to the transition structures in Figure 5.
  • 44
    • 0000351167 scopus 로고
    • It was previously reported that the disrotatory "transition state" for the cyclobutene-butadiene interconversion is actually a second-order saddle point; see: J. Breulet, H. F. Schaefer III, J. Am. Chem. Soc. 1984, 106, 1221-1226.
    • (1984) J. Am. Chem. Soc. , vol.106 , pp. 1221-1226
    • Breulet, J.1    Schaefer III, H.F.2
  • 45
    • 0034895710 scopus 로고    scopus 로고
    • It was shown previously that formally forbidden electrocyclic transition structures can be stabilized significantly through complexation to certain transition metals; see: D. J. Tantillo, R. Hoffmann, Helv. Chim. Acta 2001, 84, 1396-1404; D. J. Tantillo, R. Hoffmann, J. Am. Chem. Soc. 2001, 123, 9855-9859, and references therein.
    • (2001) Helv. Chim. Acta , vol.84 , pp. 1396-1404
    • Tantillo, D.J.1    Hoffmann, R.2
  • 46
    • 0035840977 scopus 로고    scopus 로고
    • and references therein
    • It was shown previously that formally forbidden electrocyclic transition structures can be stabilized significantly through complexation to certain transition metals; see: D. J. Tantillo, R. Hoffmann, Helv. Chim. Acta 2001, 84, 1396-1404; D. J. Tantillo, R. Hoffmann, J. Am. Chem. Soc. 2001, 123, 9855-9859, and references therein.
    • (2001) J. Am. Chem. Soc. , vol.123 , pp. 9855-9859
    • Tantillo, D.J.1    Hoffmann, R.2
  • 47
    • 0347611136 scopus 로고    scopus 로고
    • note
    • We say "partially" because the Jahn-Teller-like situation in the forbidden transition structure is replaced upon protonation by a second-order Jahn-Teller system.
  • 48
    • 0037039921 scopus 로고    scopus 로고
    • High-energy, but real, transition structures for formally forbidden suprafacial [1,7] shifts over cycloheptatriene were previously described; see: T. Okajima, K. Imafuku, J. Org. Chem. 2002, 67, 625-632.
    • (2002) J. Org. Chem. , vol.67 , pp. 625-632
    • Okajima, T.1    Imafuku, K.2
  • 49
    • 0000387311 scopus 로고
    • The effects of substituents on the stereochemical preferences of sigmatropic shifts have been discussed previously; see: M. T. Zoeckler, B. K. Carpenter, J. Am. Chem. Soc. 1981, 103, 7661-7663 and N. D. Epiotis, J. Am. Chem. Soc. 1973, 95, 1206-1214.
    • (1981) J. Am. Chem. Soc. , vol.103 , pp. 7661-7663
    • Zoeckler, M.T.1    Carpenter, B.K.2
  • 50
    • 0347611135 scopus 로고
    • The effects of substituents on the stereochemical preferences of sigmatropic shifts have been discussed previously; see: M. T. Zoeckler, B. K. Carpenter, J. Am. Chem. Soc. 1981, 103, 7661-7663 and N. D. Epiotis, J. Am. Chem. Soc. 1973, 95, 1206-1214.
    • (1973) J. Am. Chem. Soc. , vol.95 , pp. 1206-1214
    • Epiotis, N.D.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.