Competing thermal electrocyclic ring-closure reactions of (2Z)-Hexa-2,4,5-trienals and their schiff bases. Structural, kinetic, and computational studies

Journal of Organic Chemistry

Volumn 75, Issue 13, 2010, Pages 4453-4462

  Souto, José A ^a   Pérez, Martín ^a   Silva López, Carlos ^a   Álvarez, Rosana ^a   Torrado, Alicia ^a   De Lera, Angel R ^a  

^a UNIVERSITY OF VIGO   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYLIDENES; COMPUTATIONAL STUDIES; CYCLIZATIONS; DENSITY FUNCTIONAL THEORY CALCULATIONS; DIFFERENTIAL EVOLUTION; ELECTROCYCLIC RINGS; ELECTROCYCLIZATION; HETEROCYCLES; IMINE FORMATION; N-BUTYLAMINE; REACTION TIME; SCHIFF BASIS; SCHIFF-BASE DERIVATIVES; STERIC INTERACTIONS; TERT-BUTYL GROUP; TORQUOSELECTIVITY;

ACTIVATION ENERGY; CYCLIZATION; DENSITY FUNCTIONAL THEORY; EVOLUTIONARY ALGORITHMS; FUNCTIONAL GROUPS; GLOBAL OPTIMIZATION; ISOMERS; ORGANIC POLYMERS;

REACTION RATES;

ALDEHYDE DERIVATIVE; ALKYLIDENE 2H PYRAN DERIVATIVE; ALKYLIDENEPYRIDINE DERIVATIVE; BUTYLAMINE; IMINE; PYRAN DERIVATIVE; PYRIDINE DERIVATIVE; SCHIFF BASE; UNCLASSIFIED DRUG; VINYLALLENAL DERIVATIVE;

ADDITION REACTION; ARTICLE; CHEMICAL INTERACTION; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; DENSITY FUNCTIONAL THEORY; ELECTROCHEMICAL ANALYSIS; ISOMER; REACTION TIME; RING CLOSURE; RING OPENING; STRUCTURE ANALYSIS; SUBSTITUTION REACTION; SYNTHESIS; THERMODYNAMICS;

EID: 77954117697     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo100558p     Document Type: Article

References (119)

1. Silva López, C.; Álvarez, R.; Domínguez, M.; Nieto Faza, O.; de Lera, A. R. J. Org. Chem. 2009, 74, 1007
2. de Lera, A. R.; Torrado, A.; García, J.; López, S. Tetrahedron Lett. 1997, 38, 7421
3. de Lera, A. R.; Alvarez, R.; Lecea, B.; Torrado, A.; Cossío, F. P. Angew. Chem., Int. Ed. 2001, 40, 557
4. de Lera, A. R.; Cossío, F. P. Angew. Chem., Int. Ed. 2002, 41, 1150
5. Houk, K. N. Stereoselective electrocyclizations and sigmatropic shifts of strained rings: Torquoelectronics. In Strain and Its Implications in Organic Chemistry; Kluwer Academic Publishers: Dordrecht, 1989; pp 25 - 37. For reviews, see
6. Houk, K. N.; Li, Y.; Evanseck, J. D. Angew. Chem., Int. Ed. Engl. 1992, 31, 682
7. Dolbier, W. R., Jr.; Koroniak, H.; Houk, K. N.; Sheu, C. Acc. Chem. Res. 1996, 29, 471
8. 1H NMR spectra throughout the entire experiment, it was surmised to be an intermediate on route to 5a.
9. de Lera, A. R.; García, J.; Hrovat, D. A.; Iglesias, B.; López, S. Tetrahedron Lett. 1997, 38, 7425
10. Iglesias, B.; de Lera, A. R.; Rodríguez, J.; López, S. Chem. - Eur. J. 2000, 6, 4021
11. López, S.; Rodríguez, J.; García, J.; de Lera, A. R. J. Am. Chem. Soc. 1996, 118, 1881
12. Lipshutz, B. H. Synthesis 1987, 325
13. Lipshutz, B. H. Synlett 1990, 119
14. Lipshutz, B. H.; Sengupta, S. Org. React. (N. Y.) 1992, 41, 135
15. Krause, N.; Gerold, A. Angew. Chem., Int. Ed. Engl. 1997, 36, 187
16. Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.; de Meijere, A.; Diederich, F., Eds.; Wiley-VCH: Weinheim, 2004.
17. Nicolaou, K. C.; Bulger, P. G.; Sarlah, D. Angew. Chem., Int. Ed. 2005, 44, 4442
18. Piers, E.; McEachern, E. J.; Romero, M. A. Tetrahedron Lett. 1996, 37, 1173
19. Corey, E. J.; Boaz, N. W. Tetrahedron Lett. 1984, 25, 3055
20. Vaz, B.; Pereira, R.; Pérez, M.; Álvarez, R.; de Lera, A. R. J. Org. Chem. 2008, 73, 6534
21. Alkylidene-2 H -pyrans have rarely been described in the chemical literature, and references to the parent system relate merely to its role as the α-anhydro conjugate base of pyrilium salts. The elusive nature of these cyclic enol ethers is most likely due to the tendency of their reactive exocyclic alkene moiety to protonate in the presence of acid. Compounds substituted on the pyran ring with an electron-withdrawing group and/or in conjugation with phenyl substituents have extended lifetimes, allowing the incorporation of this structural subunit in pyrilium dyes. See: Reynolds, G. A.; Drexhage, K. H. J. Org. Chem. 1977, 42, 885
22. 3, are also stable: Wallace, D. J.; Sidda, R. L.; Reamer, R. A. J. Org. Chem. 2007, 72, 1051
23. An activation energy for the electrocyclic ring closure of isolated systems 2b-g could not be determined because of its decomposition upon attempted purification. The value obtained with the unpurified reaction residue for the conversion of 2g to E-3g cannot be taken rigourously due to potential complications of soluble impurities from the reagents on the kinetics of the process.
24. No direct transformation of E-3 to Z-5 is possible without the involvement of the intermediate species 2 and 4, and the direct double bond isomerization of alkylidene-2 H -pyrans was found by DFT computations (not shown) to be noncompetitive with the transformations described in Scheme 1.
25. Walter, E.; Pronzato, L. Identification of Parametric Models from Experimental Data; Springer: Masson, 1997.
26. Balsa-Canto, E.; Banga, J. R. Advanced Model Identification Using Global Optimization, 9th International Conference in Systems Biology (ICSB2008), Göteborg, 2008.
27. Storn, R.; Price, K. J. Global Optim. 1997, 11, 341
28. For all starting materials discussed, only the structures and energies of the relevant (those from which cyclization must occur) cZg conformer are provided (see Supporting Information).
29. See, for example: Braga, A. A. C.; Ujaque, G.; Maseras, F. Organometallics 2006, 25, 3647
30. Sumimoto, N.; Iwane, T.; Takahama, S.; Sakaki J. Am. Chem. Soc. 2004, 126, 10457
31. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
32. Goldstein, E.; Beno, B.; Houk, K. N. J. Am. Chem. Soc. 1996, 118, 6036
33. Houk, K. N.; Beno, B. R.; Nendel, M.; Black, K.; Yoo, H. Y.; Wilsey, S.; Lee, J. K. J. Mol. Struct. (Theochem) 1997, 398-399, 169
34. Rodríguez-Otero, J. J. Org. Chem. 1999, 64, 6842
35. Schaefer, A.; Horn, H.; Ahlrichs, R. J. Chem. Phys. 1992, 97, 2571
36. Grimme, S. J. Chem. Phys. 2006, 124, 034108
37. Grimme, S. J. Comput. Chem. 2004, 25, 1463
38. Grimme, S. J. Comput. Chem. 2006, 27, 1787
39. Weigend, F.; Häser, M. Theor. Chem. Acc. 1997, 97, 331
40. Weigend, F.; Köhn, A.; Hättig, C. J. Chem. Phys. 2002, 116, 3175
41. http://www.thch.uni-bonn.de/tc/orca/.
42. The electrocyclization reaction for the iminium ion, which could have been formed in the condensation reaction by the acidic nature of the molecular Sieves, was also computed in one case (f). The activation barriers of 27.5 and 28.6 kcal/mol, for the formation of the E and Z dihydropyridinium ion respectively, are much larger than those found for the unprotonated imine (14.7 and 15.5 kcal/mol). The values for the iminium ion are close to those determined for the Z isomers of the Schiff bases, which would evolve by a classical disrotatory electrocyclic reaction.
43. The activation energies were also computed at the same level using the M06-2X functional: Zhao, Y.; Schultz, N. E.; Truhlar, D. G. J. Chem. Theory Comput. 2006, 2, 364
44. Zhao, Y.; Truhlar, D. G. J. Chem. Phys. 2006, 125, 194101
45. Zhao, Y.; Truhlar, D. G. J. Phys. Chem. A 2006, 110, 13126
46. Zhao, Y.; Truhlar, D. G. J. Chem. Theory Comput. 2009, 5, 324
47. - (M06-2X) = 0.69 kcal/mol.
48. Bond, D. J. Org. Chem. 1990, 55, 661
49. Jensen, F. J. Am. Chem. Soc. 1995, 117, 7487
50. Tomasi, J.; Persico, M. Chem. Rev. 1994, 94, 2027
51. Mineva, T.; Russo, N.; Sicilia, E. J. Comput. Chem. 1998, 19, 290
52. Cossi, M.; Scalmani, G.; Rega, N.; Barone, V. J. Chem. Phys. 2002, 117, 43
53. Tomasi, J.; Mennucci, B.; Cammi, R. Chem. Rev. 2005, 105, 2999
54. Takano, Y.; Houk, K. N. J. Chem. Theory Comput. 2005, 1, 70
55. Rodríguez-Otero, J.; Cabaleiro-Lago, E. M. Angew. Chem., Int. Ed. 2002, 41, 1147
56. Rodríguez-Otero, J.; Cabaleiro-Lago, E. M. Chem.-Eur. J. 2003, 9, 1837
57. Cabaleiro-Lago, E. M.; Rodríguez-Otero, J.; García- López, R. M.; Peña-Gallego, A.; Hermida-Ramón, J. M. Chem.-Eur. J. 2005, 11, 5966
58. Silva López, C.; Nieto Faza, O.; Cossío, F. P.; York, D. M.; de Lera, A. R. Chem.-Eur. J. 2005, 11, 1734
59. Matito, E.; Solá, M.; Durán, M.; Poater, J. J. Phys. Chem. B 2005, 109, 7591
60. Matito, E.; Poater, J.; Durán, M.; Solá, M. ChemPhysChem 2006, 7, 111
61. Chamorro, E. E.; Notario, R. J. Phys. Chem. A 2004, 108, 4099
62. Chamorro, E. E.; Notario, R. J. Phys. Chem. B 2005, 109, 7594
63. Duncan, J. A.; Calkins, D. E. G.; Chavarha, M. J. Am. Chem. Soc. 2008, 130, 6740
64. Sakai, S. Theor. Chem. Acc. 2008, 120, 177
65. Ross, J. A.; Seiders, R. P.; Lemal, D. M. J. Am. Chem. Soc. 1976, 98, 4325
66. Bushweller, C. H.; Ross, J. A.; Lemal, D. M. J. Am. Chem. Soc. 1977, 99, 629
67. Mention of pseudopericyclic reactions can be found, in addition to refs 35, 37, and 38, in the following: Burke, L. A.; Elguero, J.; Leroy, G.; Sana, M. J. Am. Chem. Soc. 1976, 98, 1685
68. Henriksen, U.; Snyder, J. P.; Halgren, T. A. J. Org. Chem. 1981, 46, 3767
69. Okamura, W. H.; Peter, R.; Reischl, W. J. Am. Chem. Soc. 1985, 107, 1034
70. Elnagar, H.; Okamura, W. H. J. Org. Chem. 1988, 53, 3060
71. Wentrup, C.; Netsch, K.-P. Angew. Chem., Int. Ed. Engl. 1984, 23, 802
72. Koch, R.; Wong, M. W.; Wentrup, C. J. Org. Chem. 1996, 61, 6809
73. Bibas, H.; Koch, R.; Wentrup, C. J. Org. Chem. 1998, 63, 2629
74. Ham, S.; Birney, D. M. Tetrahedron Lett. 1994, 35, 8113
75. Birney, D. M.; Wagenseller, P. E. J. Am. Chem. Soc. 1994, 116, 6262
76. Birney, D. M. J. Org. Chem. 1994, 59, 2557
77. Wagenseller, P. E.; Birney, D. M.; Roy, D. J. Org. Chem. 1995, 60, 2853
78. Birney, D. M. J. Org. Chem. 1996, 61, 243
79. Birney, D. M.; Ham, S.; Unruh, G. R. J. Am. Chem. Soc. 1997, 119, 4509
80. Birney, D. M.; Xu, X. L.; Ham, S.; Huang, X. M. J. J. Org. Chem. 1997, 62, 7114
81. Quideau, S.; Looney, M. A.; Pouységu, L.; Ham, S.; Birney, D. M. Tetrahedron Lett. 1999, 40, 615
82. Birney, D. M.; Xu, X. L.; Ham, S. Angew. Chem., Int. Ed. 1999, 38, 189
83. Shunway, W.; Ham, S.; Moer, J.; Whittlesey, B. R.; Birney, D. M. J. Org. Chem. 2000, 65, 7731
84. Birney, D. M. J. Am. Chem. Soc. 2000, 122, 10917
85. Bartsch, R. A.; Chae, Y. M.; Ham, S.; Birney, D. M. J. Am. Chem. Soc. 2001, 123, 7479
86. Zhou, C.; Birney, D. M. J. Am. Chem. Soc. 2002, 124, 5231
87. Birney, D. M. Org. Lett. 2004, 6, 851
88. Wei, H.-X.; Zhou, C.; White, J. M.; Birney, D. M. Org. Lett. 2004, 6, 4289
89. Ji, H.; Xu, X.; Ham, S.; Hammad, L. A.; Birney, D. M. J. Am. Chem. Soc. 2009, 131, 528
90. Luo, L.; Barberger, M. D.; Dolbier, W. R., Jr. J. Am. Chem. Soc. 1997, 119, 12366
91. Fabian, W. M. F.; Bakulev, V. A.; Kappe, C. O. J. Org. Chem. 1998, 63, 5801
92. Fabian, W. M. F.; Kappe, C. O.; Bakulev, V. A. J. Org. Chem. 2000, 65, 47
93. Alajarín, M.; Vidal, A.; Sánchez-Andrada, P.; Tovar, F.; Ochoa, G. Org. Lett. 2000, 2, 965
94. Rodríguez-Otero, J.; Cabaleiro-Lago, E. M.; Hermida-Ramón, J. M.; Peña-Gallego, A. J. Org. Chem. 2003, 68, 8823
95. Cabaleiro-Lago, E. M.; Rodríguez-Otero, J.; Hermida-Ramón, J. M. J. Phys. Chem. A 2003, 107, 4962
96. Cabaleiro-Lago, E. M.; Rodríguez-Otero, J.; Varela-Varela, S. M.; Peña-Gallego, A.; Hermida-Ramón, J. M. J. Org. Chem. 2005, 70, 3921
97. Alajarín, M.; Sánchez-Andrada, P.; Vidal, A.; Tovar, F. J. Org. Chem. 2005, 70, 1340
98. Alajarín, M.; Ortín, M. M.; Sánchez-Andrada, P.; Vidal, A.; Bautista, D. Org. Lett. 2005, 7, 5281
99. Alajarín, M.; Sánchez-Andrada, P.; López-Leonardo, C.; Álvarez, A. J. Org. Chem. 2005, 70, 7617
100. Peña-Gallego, A.; Rodríguez-Otero, J.; Cabaleiro-Lago, E. M. Eur. J. Org. Chem. 2005, 70, 3228
101. Rode, J. E.; Dobrowolski, J. C. J. Phys. Chem. A 2006, 110, 207
102. Rode, J. E.; Dobrowolski, J. C. Chem. Phys. Lett. 2007, 449, 240
103. Calvo-Losada, S.; Quirante Sánchez, J. J. J. Phys. Chem. A 2008, 112, 8164
104. Jones, G. O.; Li, X.; Hayden, A. E.; Houk, K. N.; Danishefsky, S. J. Org. Lett. 2008, 10, 4093
105. Alajarín, M.; Bonillo, B.; Sánchez-Andrada, P.; Vidal, A.; Bautista, D. Org. Lett. 2009, 11, 1365
106. Forte, L.; Lafortune, M. C.; Bierzynski, I. R.; Duncan, J. A. J. Am. Chem. Soc. 2010, 132, 2196
107. Schiess, P.; Chia, H. L. Helv. Chim. Acta 1970, 53, 485
108. Schiess, P.; Seeger, R.; Suter, C. Helv. Chim. Acta 1970, 53, 1713
109. For a DFT study of 2,4-pentadienals and 2 H -pyrans, see: Wang, Z.; Day, P. N.; Pachter, R. Chem. Phys. Lett. 1995, 237, 45-52
110. Wang, Z.; Day, P. N.; Pachter, R. J. Phys. Chem. 1995, 99, 9730
111. Maynard, D. F.; Okamura, W. H. J. Org. Chem. 1995, 60, 1763
112. The activation energies for the ring closure of the parent (2 Z)-hexa-1,3,5-triene to cyclohexa-1,3-diene are on the order of 30 kcal/mol. Lewis, K. E.; Steiner, H. J. Chem. Soc. 1964, 3080
113. Marvell, E. N.; Caple, G.; Schatz, B. Tetrahedron Lett. 1965, 385
114. Vogel, E.; Grimme, W.; Dinné, E. Tetrahedron Lett. 1965, 391
115. Marvell, E. N.; Caple, G.; Schatz, B.; Pippin, W. Tetrahedron Lett. 1973, 29, 3781
116. Highly substituted systems containing the dienylallene substructure have been found to cyclize below room temperature to provide the corresponding alkylidenecyclohexadienes: Reischl, W.; Okamura, W. H. J. Am. Chem. Soc. 1982, 104, 6115
117. Okamura, W. H.; Peter, R.; Reischl, W. J. Am. Chem. Soc. 1985, 107, 1034
118. Elnagar, H. Y.; Okamura, W. H. J. Org. Chem. 1988, 53, 3060
119. The subset of molecular rearrangements that contain a single disconnection in the cyclic array of orbitals and therefore only require a monorotatory movement of the terminus along the reaction coordinate to assist the development of the new s-bond were shown to have pseudopericyclic features. See ref. 40 for a general discussion and ref. 41a for computational analysis of a monorotatory pseudopericyclic electrocyclization.