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Gill, P.M.W.2
Pople, J.A.3
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86
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0344383355
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Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montogomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J., Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Repogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; DeFrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzales, M. C.; Pople, J. A.; Gaussian Program, Gaussian 94, Rev. B1 and D4, Gaussian, Inc.; Pittsburgh, PA, 1995.
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(1995)
Gaussian Program, Gaussian 94
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Frisch, M.J.1
Trucks, G.W.2
Schlegel, H.B.3
Gill, P.M.W.4
Johnson, B.G.5
Robb, M.A.6
Cheeseman, J.R.7
Keith, T.8
Petersson, G.A.9
Montogomery, J.A.10
Raghavachari, K.11
Al-Laham, M.A.12
Zakrzewski, V.G.13
Ortiz, J.V.14
Foresman, J.B.15
Cioslowski, J.16
Stefanov, B.B.17
Nanayakkara, A.18
Challacombe, M.19
Peng, C.Y.20
Ayala, P.Y.21
Chen, W.22
Wong, M.W.23
Andres, J.L.24
Repogle, E.S.25
Gomperts, R.26
Martin, R.L.27
Fox, D.J.28
Binkley, J.S.29
Defrees, D.J.30
Baker, J.31
Stewart, J.P.32
Head-Gordon, M.33
Gonzales, M.C.34
Pople, J.A.35
more..
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89
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0000571374
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3 bond. Experiments (Blom, C. E.; Günthard, Hs. H. Chem. Phys. Lett. 1981, 84, 267) and calculations (Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1988, 110, 1870-1872. Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872-1874) likewise show that the Z- conformations of esters are more stable than the E-conformations by 5-10 kcal/mol, due to unfavorable dipolar interactions in the latter.
-
(1981)
Chem. Phys. Lett.
, vol.84
, pp. 267
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-
Blom, C.E.1
Günthard, H.H.2
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90
-
-
0001651476
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-
3 bond. Experiments (Blom, C. E.; Günthard, Hs. H. Chem. Phys. Lett. 1981, 84, 267) and calculations (Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1988, 110, 1870-1872. Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872-1874) likewise show that the Z- conformations of esters are more stable than the E-conformations by 5-10 kcal/mol, due to unfavorable dipolar interactions in the latter.
-
(1988)
J. Am. Chem. Soc.
, vol.110
, pp. 1870-1872
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-
Wang, X.1
Houk, K.N.2
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91
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33845278614
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3 bond. Experiments (Blom, C. E.; Günthard, Hs. H. Chem. Phys. Lett. 1981, 84, 267) and calculations (Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1988, 110, 1870-1872. Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872-1874) likewise show that the Z-conformations of esters are more stable than the E-conformations by 5-10 kcal/mol, due to unfavorable dipolar interactions in the latter.
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(1988)
J. Am. Chem. Soc.
, vol.110
, pp. 1872-1874
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Wiberg, K.B.1
Laidig, K.E.2
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92
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0344383354
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note
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vjb for the other vibrations. Note that, due to the small entropy and heat capacity differences between the different conformers, ΔG will not exhibit a strong temperature dependence.
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-
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93
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0029931111
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Sander, W.; Kirschfeld, A.; Kappert, W.; Muthusamy, S.; Kiselewsky, M. J. Am. Chem. Soc. 1996, 118, 6508.
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(1996)
J. Am. Chem. Soc.
, vol.118
, pp. 6508
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Sander, W.1
Kirschfeld, A.2
Kappert, W.3
Muthusamy, S.4
Kiselewsky, M.5
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96
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0344815067
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note
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2 7839 G.; microwave frequency 9.510 GHz.
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-
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97
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0043091666
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-
Wasserman, E.; Snyder, L. C.; Yager, W. A. J. Chem. Phys. 1964, 41, 1763.
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(1964)
J. Chem. Phys.
, vol.41
, pp. 1763
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-
Wasserman, E.1
Snyder, L.C.2
Yager, W.A.3
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98
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0001401554
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-
Trozzolo, A. M.; Wasserman, E.; Yager, W. A. J. Am. Chem. Soc. 1965, 87, 129.
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(1965)
J. Am. Chem. Soc.
, vol.87
, pp. 129
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-
Trozzolo, A.M.1
Wasserman, E.2
Yager, W.A.3
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100
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0344383352
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note
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2 transitions were coincident with the corresponding transitions of the major rotamer
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-
-
-
102
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0344383350
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25 Since the point spin model is not appropriate to analyze the NCC isomers, the assumption of treating the effects of the substituents on the D values as additive represents an oversimplification
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25 Since the point spin model is not appropriate to analyze the NCC isomers, the assumption of treating the effects of the substituents on the D values as additive represents an oversimplification.
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-
-
-
103
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0344383349
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-
Note that, by virtue of the substituent priorities in the Cahn-Ingold-Prelog rules, there is a "reversal" in the E/Z-nomeclature in going from MDA to NCC. Thus, (E,E)-MDA yields (Z,Z)-NCC and (E,Z)-MDA gives (Z,E)-NCC (and vice versa)
-
Note that, by virtue of the substituent priorities in the Cahn-Ingold-Prelog rules, there is a "reversal" in the E/Z-nomeclature in going from MDA to NCC. Thus, (E,E)-MDA yields (Z,Z)-NCC and (E,Z)-MDA gives (Z,E)-NCC (and vice versa).
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-
-
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104
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0344815066
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92
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92
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-
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105
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0006597865
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See, e.g.: Albers, R.; Sander, W.; Ottoson, C.-H.; Cremer, D. Chem. Eur. J. 1996, 2, 967.
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(1996)
Chem. Eur. J.
, vol.2
, pp. 967
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Albers, R.1
Sander, W.2
Ottoson, C.-H.3
Cremer, D.4
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106
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0344383348
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-
note
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78 Our value of ΔE(BCH-BHT) = 3.0 kcal/mol disagrees with the value of 1.4 kcal/mol which can be gathered from Table 2 of ref 78 (both by B3LYP/6-31G* after ZPE correction). The reason is that for BCH (16 in the previous study) the ZPE difference of 0.8 kcal/mol was subtracted instead of added to the energy difference to triplet 2-naphthyl-carbene. The B3LYP/6-31G* entry for 16 should be 3.4 kcal/mol instead of 1.8 kcal/mol.
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-
-
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107
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0344815065
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note
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72b even B3LYP appears to overestimate the barriers for such reactions.
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-
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108
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0345677848
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72b we found ∼48 h at 12 K
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72b we found ∼48 h at 12 K.
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-
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111
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0345677846
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-
note
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105 As this was too expensive to perform for the naphthyl system, we resorted to the corresponding phenyl derivative, which shows a saddle point of very similar structure associated with a similar activation energy relative to the (carbomethoxy)carbene (30.2 kcal/mol). An IRC calculation starting from 1-phenyl-2-methoxyoxirene did indeed show a smooth descent to phenyl(carbomethoxy)carbene in one direction and to benzoyl(methoxy-)carbene in the other direction. We can see no reason this should be different in the naphthyl system.
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-
-
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113
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0345677845
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note
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0 = -6.0 kcal/mol) takes on a two-step course via a shallow oxirene minimum of much lower relative energy. A more in-depth study of this phenomenon is in progress (Matzinger, S.; Bally, T., to be published).
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-
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114
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0043109854
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Strausz, O. P.; Gosavi, R. K.; Denes, A. S.; Czismadia, I. G. J. Am. Chem. Soc. 1976, 98, 4784.
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(1976)
J. Am. Chem. Soc.
, vol.98
, pp. 4784
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Strausz, O.P.1
Gosavi, R.K.2
Denes, A.S.3
Czismadia, I.G.4
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115
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0030896462
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Bush, L. C.; Heath, R. B.; Feng, X. W.; Wang, P. A.; Maksimovic, L.; Song, A. I.; Chung, W.-S.; Berinstain, A. B.; Scaiano, J. C.; Berson, J. A. J. Am. Chem. Soc. 1997, 119, 1406.
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(1997)
J. Am. Chem. Soc.
, vol.119
, pp. 1406
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-
Bush, L.C.1
Heath, R.B.2
Feng, X.W.3
Wang, P.A.4
Maksimovic, L.5
Song, A.I.6
Chung, W.-S.7
Berinstain, A.B.8
Scaiano, J.C.9
Berson, J.A.10
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116
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0030895105
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Bush, L. C.; Maksimovic, L.; Feng, X. W.; Lu, H. S. M.; Berson, J. A. J. Am. Chem. Soc. 1997, 119, 1416.
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J. Am. Chem. Soc.
, vol.119
, pp. 1416
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-
Bush, L.C.1
Maksimovic, L.2
Feng, X.W.3
Lu, H.S.M.4
Berson, J.A.5
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117
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0344383347
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108,109 Consequently, they lack a thermochemical driving force tor S → T or T → S conversion which could be part of the reason it is not observed
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108,109 Consequently, they lack a thermochemical driving force tor S → T or T → S conversion which could be part of the reason it is not observed.
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-
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118
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0345677843
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note
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2 moiety is preserved in the first excited state.
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-
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120
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0001474841
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β-Lactone formation has been observed previously on thermolysis of diazo esters: Richardson, D. C.; Hendrick, M. E.; Jones, M. J. Am. Chem. Soc. 1971, 93, 3790.
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(1971)
J. Am. Chem. Soc.
, vol.93
, pp. 3790
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-
Richardson, D.C.1
Hendrick, M.E.2
Jones, M.3
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