On the origins of diastereofacial selectivity in Diels-Alder cycloadditions

Synlett

Volumn , Issue 11, 1999, Pages 1681-1703

  Coxon, James M ^a   Froese, Robert D J ^b   Ganguly, Bishwajit ^c   Marchand, Alan P ^c   Morokuma, Keiji ^b  

^a UNIVERSITY OF CANTERBURY   (New Zealand)

^b EMORY UNIVERSITY   (United States)

^c UNIVERSITY OF NORTH TEXAS   (United States)

Author keywords

Ab initio; Acetylene Diels Alder; Cage compounds; Correlation diagram; Ethylene Diels Alder; Facial selectivity; Semi empirical

Indexed keywords

ACETYLENE; ETHYLENE;

CALCULATION; CHEMICAL REACTION; REVIEW; STEREOCHEMISTRY;

EID: 0032756941     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-2920     Document Type: Review

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72. C-C)
73. Coxon, J.M.; McDonald, D.Q. Tetrahedron Lett. 1992, 33, 651.
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75. For an alternative explanation involving the "orbital mixing rule" see: Ishida, M.; Beniya, Y.; Inagaki, S.; Kato, K. J. Am. Chem. Soc. 1990, 112, 8981.
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80. Coxon, J. M.; O'Connell, M.J.; Steel, P.J. Acta Cryst. 1986, 1773. Dhaneshwar, N. N.; Tavale, S. S.; Guru Row, T. N.; Zope, U. R.; Pandey, B.; Ayyangar, N. R. Acta Crystallogr. Sect. C: Cryst. Struct. Commun. 1988, 44, 2191.
81. This report Tolstikov, G.A.; Lerman, B.M; Galin, F. Z. Zh. Org. Khim. 1975, 11, 1348 suggested that p-benzoquinone added to 4 exclusively from the face anti to the carbonyls. A later re-examination of this reaction has determined this to be incorrect.
82. Coxon, J. M.; O'Connell, M. J.; Steel, P. J. J. Org. Chem. 1987, 52, 4726.
83. Pandey, B.; Zope, U. R.; Ayyangar, N. R. Synth. Commun. 1989, 19, 585.
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89. Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902. MOPAC, version 6.0. Quantum Chemistry Program Exchange (QCPE), Program Number 455, 1990.
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92. Mehta, G.; Karra, S. R. J. Org. Chem. 1989, 54, 2975,
93. (b) Mehta, G.; Padma, S.; Pattabhi, V.; Pramanik, A.; Chandrasekhar, J. J. Am. Chem. Soc. 1990, 112, 2942.
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96. Marchand, A. P.; Dong, E. Z.; Shukla, R.; Prasad, A. D.; Bott, S. G. Tetrahedron 1997, 53, 14895.
97. Conditions: benzene solvent, reflux 7 days.
98. Marchand, A. P.; Ganguly, B.; Shukla, R. Tetrahedron 1998, 54, 4477.
99. Synchronous transition state is one where the two newly-formed σ-bonds in the transition structure are formed to the same extent. A concerted Diels-Alder cycloaddition between an unsymmetrical diene and either a symmetrical or an unsymmetrical dienophile is expected to proceed via an asynchronous transition state in which the two newly-formed σ-bonds in the transition structure most probably are not formed to the same extent.
100. Coxon, J. M.; Fong, S. T.; Steel,; P.J.; Bott, S.G.; Marchad, A. P.; Zope, U. R. Acta Cryst. 1993, C49, 1859. Mehta, G.; Singh, V.; Rao, K. S. Tetrahedron Lett. 1980, 21, 1369.
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102. Marchand, A. P.; Shukla, R.; Burritt, A.; Bott, S. G. Tetrahedron 1995, 51, 8733.
103. Marchand, A. P.; Zope, U. R.; Burritt, A.; Bott, S. G.; Coxon, J. Tetrahedron 1995, 34, 9319.
104. Boger, D. Chem. Rev. 1986, 86, 781.
105. The MMX force-field contained within PCMODEL, version 4.0, available from Serena Software, Box 3076, Bloomington, IN 47402-3076, was used for these calculations.
106. Coxon, J. M.; Fong, S.T,; McDonald, D. Q.; Steel, P.J. Tetrahedron Lett. 1993, 34, 163.
107. Coxon, J.M.; McDonald, D.Q. Tetrahedron Letters. 1991, 32, 7115.
108. Humbel, S. ; Sieber, S. ; Morokuma, K. J. Chem. Phys. 1996, 105, 1959. Svensson, M.; Humbel, S. ; Morokuma, K. J. Chem. Phys. 1996, 105, 3654.
109. Humbel, S. ; Sieber, S. ; Morokuma, K. J. Chem. Phys. 1996, 105, 1959. Svensson, M.; Humbel, S. ; Morokuma, K. J. Chem. Phys. 1996, 105, 3654.
110. Coxon, J. M.; Siew Tai Fong; McDonald, D. Q.; O'Connell, M. J.; Steel, P. J. Tetrahedron Lett. 1991, 32, 7115. McCarrick, M. A.; Wu, Y.-D.; Houk, K. N. J. Am. Chem. Soc. 1992, 114, 1499.
111. Coxon, J. M.; Siew Tai Fong; McDonald, D. Q.; O'Connell, M. J.; Steel, P. J. Tetrahedron Lett. 1991, 32, 7115. McCarrick, M. A.; Wu, Y.-D.; Houk, K. N. J. Am. Chem. Soc. 1992, 114, 1499.
112. Maleic anhydride reacted on the less hindered face syn to the ether group while the acetylene species DMAD adds anti to the oxygen. This was considered a result of repulsion between the lone pairs on the oxygen and the p-orbital of the acetylene orthogonal to the reacting p-orbital. N-phenyltriazolinedione (PTAD) also adds from the more sterically hindered face and lone pair-lone pair interactions may destabilize the transition state syn to the ether oxygen.
113. Svensson, M.; Humbel, S.; Froese, R. D. J.; Matsubara, T.; Sieber, S.; Morokuma, K. J. Phys. Chem. 1996, 100, 19357. Maseras, F.; Morokuma, K. J. Comput. Chem. 1995, 16, 1170. Matsubara, T.; Maseras, F.; Koga, N.; Morokuma, K. J. Phys. Chem. 1996, 100, 2573.
114. Svensson, M.; Humbel, S.; Froese, R. D. J.; Matsubara, T.; Sieber, S.; Morokuma, K. J. Phys. Chem. 1996, 100, 19357. Maseras, F.; Morokuma, K. J. Comput. Chem. 1995, 16, 1170. Matsubara, T.; Maseras, F.; Koga, N.; Morokuma, K. J. Phys. Chem. 1996, 100, 2573.
115. Svensson, M.; Humbel, S.; Froese, R. D. J.; Matsubara, T.; Sieber, S.; Morokuma, K. J. Phys. Chem. 1996, 100, 19357. Maseras, F.; Morokuma, K. J. Comput. Chem. 1995, 16, 1170. Matsubara, T.; Maseras, F.; Koga, N.; Morokuma, K. J. Phys. Chem. 1996, 100, 2573.
116. Svensson, M.; Humbel, S.; Morokuma, K. J, Chem. Phys. 1996, 105, 3654. Dapprich, S.; Komáromi, I.; Byun, K. S.; Morokuma, K.; Frisch, M. J. J. Mol. Str. (Theochem) In press.
117. Svensson, M.; Humbel, S.; Morokuma, K. J, Chem. Phys. 1996, 105, 3654. Dapprich, S.; Komáromi, I.; Byun, K. S.; Morokuma, K.; Frisch, M. J. J. Mol. Str. (Theochem) In press.
118. Froese, R. D. J.; Coxon, J. M.; West, S. C.; Morokuma, K. J. Org. Chem. 1997, 62, 6991.
119. The IMOMO(G2MS:MP2) method also has been shown to reproduce regio-and stereoselectivities in Diels-Alder reactions satisfactorily.
120. real - [MP2/6-31G*]model} . The term in the first curly brackets represents the basis set correction to the model system and the second term represents the substituent effects at the MP2/6-31G* level. It should be noted that if the GAUSSIAN program is used, only three calculations have to be performed as for the model system, as the MP2/6-31G* is calculated within the CCSD(T)/6-31G* job.
121. real - [MP2/6-31G*]model} . The term in the first curly brackets represents the basis set correction to the model system and the second term represents the substituent effects at the MP2/6-31G* level. It should be noted that if the GAUSSIAN program is used, only three calculations have to be performed as for the model system, as the MP2/6-31G* is calculated within the CCSD(T)/6-31G* job.
122. real - [MP2/6-31G*]model} . The term in the first curly brackets represents the basis set correction to the model system and the second term represents the substituent effects at the MP2/6-31G* level. It should be noted that if the GAUSSIAN program is used, only three calculations have to be performed as for the model system, as the MP2/6-31G* is calculated within the CCSD(T)/6-31G* job.
123. real - [MP2/6-31G*]model} . The term in the first curly brackets represents the basis set correction to the model system and the second term represents the substituent effects at the MP2/6-31G* level. It should be noted that if the GAUSSIAN program is used, only three calculations have to be performed as for the model system, as the MP2/6-31G* is calculated within the CCSD(T)/6-31G* job.
124. real - [MP2/6-31G*]model} . The term in the first curly brackets represents the basis set correction to the model system and the second term represents the substituent effects at the MP2/6-31G* level. It should be noted that if the GAUSSIAN program is used, only three calculations have to be performed as for the model system, as the MP2/6-31G* is calculated within the CCSD(T)/6-31G* job.
125. real - [MP2/6-31G*]model} . The term in the first curly brackets represents the basis set correction to the model system and the second term represents the substituent effects at the MP2/6-31G* level. It should be noted that if the GAUSSIAN program is used, only three calculations have to be performed as for the model system, as the MP2/6-31G* is calculated within the CCSD(T)/6-31G* job.
126. real - [MP2/6-31G*]model} . The term in the first curly brackets represents the basis set correction to the model system and the second term represents the substituent effects at the MP2/6-31G* level. It should be noted that if the GAUSSIAN program is used, only three calculations have to be performed as for the model system, as the MP2/6-31G* is calculated within the CCSD(T)/6-31G* job.
127. real - [MP2/6-31G*]model} . The term in the first curly brackets represents the basis set correction to the model system and the second term represents the substituent effects at the MP2/6-31G* level. It should be noted that if the GAUSSIAN program is used, only three calculations have to be performed as for the model system, as the MP2/6-31G* is calculated within the CCSD(T)/6-31G* job.
128. 14 using the gradient corrected hybrid B3LYP method. Becke, A. D. J. Chem. Phys. 1993, 98, 5648. For the diene 21 the mixed 6-31G [Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, 724. Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257. Hariharan, P. C.; Pople, J. A. Mol. Phys. 1974, 27, 209. Gordon, M. S. Chem. Phys. Lett. 1980, 76, 163. Hariharan, P, C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213] and 3-21G [Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980, 102, 939. Gordon, M. S.; Binkley, J. S.; Pople, J. A.; Pietro, W. J.; Hehre, W. J. J. Am. Chem. Soc. 1982, 104, 2797. Pietro, W. J.; Franel, M. M.; Hehre, W. J.; Defrees, D. J.; Pople, J. A.; Binkley, J. S. J. Am. Chem. Soc. 1982, 104, 5039] basis sets have been employed. For 21, carbon atoms 1-9 and associated hydrogens utilized the 6-31G basis set and the atoms further from the reaction center, 10-16 and associated hydrogens used the 3-21G basis set (Figure 12). Ethylene or acetylene fragments used as part of the reactants and this moiety in both the transition state and product were treated with the 6-31G basis set. Due to the rigidity of the ring systems, this optimization should be reliable despite the smaller basis set. Nonetheless, these basis sets are smaller than 6-31G* which is recommended for B3LYP geometry optimization in conjunction with the single point G2MS energy to be used in our best
129. Entropy (free energy) and thermal corrections are not included in the calculation; however the difference between these values for syn vs. and anti addition is expected to be small, but could reflect differences between calculation and experiment.