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M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery, Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A. D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M. W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Revisions D.02 and E.01, Gaussian, Inc., Wallingford, CT, 2004.
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Montgomery Jr., J.A.7
Vreven, T.8
Kudin, K.N.9
Burant, J.C.10
Millam, J.M.11
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Hratchian, H.P.34
Cross, J.B.35
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Jaramillo, J.38
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Pomelli, C.44
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Morokuma, K.47
Voth, G.A.48
Salvador, P.49
Dannenberg, J.J.50
Zakrzewski, V.G.51
Dapprich, S.52
Daniels, A.D.53
Strain, M.C.54
Farkas, O.55
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Rabuck, A.D.57
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Cui, Q.61
Baboul, A.G.62
Clifford, S.63
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Amos, R.D.9
Bernhardsson, A.10
Berning, A.11
Cooper, D.L.12
Deegan, M.J.O.13
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Eckert, F.15
Hampel, C.16
Hetzer, G.17
Lloyd, A.W.18
McNicholas, S.J.19
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Mura, M.E.21
Nicklass, A.22
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85031206445
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According to the presentation of structure 4 in Scheme 1, the orientations of both methyl groups in 4 have been constrained during geometric optimizations, so that one methyl hydrogen atom is placed in cisoid position to the semicyclic bond (compare ref. [2])
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According to the presentation of structure 4 in Scheme 1, the orientations of both methyl groups in 4 have been constrained during geometric optimizations, so that one methyl hydrogen atom is placed in cisoid position to the semicyclic bond (compare ref. [2]).
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18
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85031209575
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First, 5 was geometrically optimized without any geometric constraint. Then the Cartesian coordinates of all the atoms of ring A have been frozen and the geometry was reoptimized with dihedral angles d1 and d2 of ring B constrained to different values, so that anti-conformations result. Syn-conformations, in which both rings bend to the same side of the double bond, are not analyzed herein
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First, 5 was geometrically optimized without any geometric constraint. Then the Cartesian coordinates of all the atoms of ring A have been frozen and the geometry was reoptimized with dihedral angles d1 and d2 of ring B constrained to different values, so that anti-conformations result. Syn-conformations, in which both rings bend to the same side of the double bond, are not analyzed herein.
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20
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85031206459
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Additionally the orientations of one CH-bond in each of the methyl groups in 6, 8, and 9 have been constrained during the geometric optimizations in order to minimize the effect of steric repulsions between hydrogen atoms, attached to the positions 1 and 3 of the CCC bond angle af. In each molecule the dihedral angles of one CH-bond was constrained to be co-planar with the respective double bond, as shown by the orientation of these methyl groups in Scheme 3
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Additionally the orientations of one CH-bond in each of the methyl groups in 6, 8, and 9 have been constrained during the geometric optimizations in order to minimize the effect of steric repulsions between hydrogen atoms, attached to the positions 1 and 3 of the CCC bond angle af. In each molecule the dihedral angles of one CH-bond was constrained to be co-planar with the respective double bond, as shown by the orientation of these methyl groups in Scheme 3.
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