Theoretical studies on pentadienyl cation electrocyclizations

Current Organic Chemistry

Volumn 14, Issue 15, 2010, Pages 1561-1577

  Davis, Rebecca L ^a   Tantillo, Dean J ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Carbocation; Electrocyclization; Nazarov; Pentadienyl; Quantum chemistry

Indexed keywords

POSITIVE IONS; SYNTHESIS (CHEMICAL);

CARBOCATIONS; COMPLEX ORGANIC MOLECULES; ELECTROCYCLIZATION; NAZAROV; PENTADIENYL; THEORETICAL STUDY;

QUANTUM CHEMISTRY;

EID: 77956405531     PISSN: 13852728     EISSN: None     Source Type: Journal    
DOI: 10.2174/138527210793563297     Document Type: Article

References (93)

1. Sorensen, T.S.; Rauk, A. In: Pericyclic Reactions; Marchand, A. P., Lehr, R. E., Eds.; New York, 1977; 11, pp. 21-34.
2. Lemiere, G.; Gandon, V.; Cariou, K.; Hours, A.; Fukuyama, T.; Dhimane, A.; Fensterbank, L.; Malacria, M. Generation and trapping of cyclopenten-ylidene gold species: four pathways to polycyclic compounds. J. Am. Chem. Soc., 2009, 131, 2939-3006.
3. Miller, A.K.; Banghart, M.R.; Beaudry, C.M.; Shu, J.M; Trauner, D. Development of novel Lewis acid catalyzed cycloisomerizations: synthesis of bicyclo[3.1.0]hexenes and cyclopentenones. Tetrahedron, 2003, 59, 8919-8930.
4. Tius, M.A.; Astrab, D.P. Cationic cyclopentannelation. synthesis of (d,1)-Xanthocidin. Tetrahedron Lett., 1989, 30, 2333-2336.
5. Tius, M.A.; Hu, H.; Kawakami, J.K.; Busch-Petersen, J. Synthesis of 15-Deoxy-12-hydroxy-10-(trifluoromethyl)-7-PGA1 methyl ester. J. Org. Chem., 1998, 63, 5971-5976.
6. Malona, J.A.; Cariou, K.; Frontier, A.J. Nazarov cyclization initiated by peracid oxidation: the total synthesis of (±)-Rocaglamide. J. Am. Chem. Soc. 2009, 131, 7560-7561.
7. Lin, C.; Teng, T.; Tsai, C.; Liao, H.; Liu, R. Gold-catalyzed deoxygenative nazarov cyclization of 2,4-Dien-1-als for stereoselective synthesis of highly substituted cyclopentenes. J. Am. Chem. Soc., 2008, 130, 16417-16423.
8. Woodward, R.B.; Hoffmann, R. Stereochemistry of electrocyclic reactions. J. Am. Chem. Soc., 1965, 87, 395-397.
9. Woodward, R.B.; Hoffmann, R. The conservation of orbital symmetry. Angew. Chem. Int. Ed., 1969, 8, 781-932.
10. Kirmse, W.; Rondan, N.G.; Houk K.N.; Stereoselective substituent effects on conrotatory electrocyclic reactions of cyclobutenes. J. Am. Chem. Soc., 1984, 106, 7989-7991.
11. Dolbier, W.R. Jr.; Koroniak, H.; Houk, K. N.; Sheu, C. Electronic control of stereoselectivities of electrocyclic reactions of cyclobutenes: a triumph of theory in the prediction of organic reactions. Acc. Chem. Res., 1996, 29, 471-477.
12. Schleyer, P.v.R.; Bentley, T.W.; Koch, W.; Kos, A.J.; Schwarz, H. Structures and energies of isomeric cyclopentenyl cations. resolution of the question of anchimeric assistance in cyclopenten-4-yl solvolysis. J. Am. Chem. Soc., 1987, 109, 6953-6957.
13. Kallel, E.A.; Houk, K.N.; Theoretical predictions of torquoselectivity in pentadienyl cation electrocyclizations. J. Org. Chem., 1989, 54, 6006-6008.
14. Houk, K.N.; Li, Y.; Evanseck, J.D. Transition structures of hydrocarbon pericyclic reactions. Angew. Chem. Int. Ed., 1992, 31, 682-708.
15. Suzuki, T.; Ohwada, T.; Shudo, K. Superacid-catalyzed electrocyclization of 1-Phenyl-2-propen-1-ones to 1-Indanones. kinetic and theoretical studies of electrocyclization of oxonium-carbenium dications. J. Am. Chem. Soc., 1997, 119, 6774-6780.
16. Goumans, T.P.M.; Ehlers, A.W.; Lammertsma, K.; Würthwein, E.-U.; Grimme, S. Improved reaction and activation energies of [4+2] cycloadditions, [3,3] sigmatropic rearrangements and electrocyclizations with the spin-component-scaled MP2 method. Chem. Eur. J., 2004, 10, 6468-6475.
17. Howell, J. A. S.; O'Leary, P. J.; Yates, P. C.; Acyclic O- and N-substituted pentadienyl cations: structural characterisation, cyclisation and computational results. Tetrahedron, 1995, 51, 7231-7246.
18. Alickmann, D.; Fröhlich, R.; Maulitz, A.H.; Würthwein, E.-U. Electrocyclization reactions of 1-Aza- and 1-Oxapentadienyl and -heptatrienyl cations: synthesis of pyrrole and furan derivatives. Eur. J. Org. Chem., 2002, 1523-1537.
19. The azapentadienyl cation cyclization was also studied with SCS-MP2/6-311++G(3df,3dp) [13]. While the geometry of the reactive intermediate was not specified, the reported activation energy (10.0 kcal/mol) and reaction energy (-57.9 kcal/mol) are consistent with results for the conversion of 6 to 8. (Fig. 4)
20. Woodward R. B. Aromaticity. The Chemical Society: London, 1968.
21. Campbell, P.H.; Chiu, N.W.K.; Deugau, K.; Miller, I.J.; Sorensen, T.S. The stereochemistry of the pentadienyl-Cyclopentenyl cation rearrangement. J. Am. Chem. Soc., 1969, 91, 6404-6410.
22. Chiu, N.W.K.; Sorensen, T.S. The direct observation of a stereospecific pentadienyl-cyclopentenyl cation cyclization. Can. J. Chem., 1973, 51, 2776-2782.
23. Bladek, R.; Sorensen, T. S. Kinetics of pentadienyl cation cyclizations. Can. J. Chem., 1972, 50, 2806-2816.
24. Denmark, S.E.; Habermas, K.L.; Hite, G.A. Silicon-Directed Nazarov Cyclizations. Part V. Substituent and heteroatom effects on the reaction. Helv. Chem. Acta, 1988, 71, 168-194.
25. While Houk examined a variety of systems using single point calculations (Ref 11a), only fully optimized systems are discussed in this review.
26. Faza, O.N.; López, C.S.; Álvarez, R.; de Lera, A.R. Theoretical Study of the electrocyclic ring closure of hydroxypentadienyl cations. Chem. Eur. J., 2004, 10, 4324-4333.
27. Chen, Z.; Wannere, C.S.; Corminboeuf, C.; Puchta, R.; Schleyer, P.v.R. Nucleus-independent chemical shifts (NICS) as an aromaticity criterion. Chem. Rev., 2005, 105, 3842-3888.
28. Faza, O.N.; López, C.S.; Álvarez, R.; de Lera, A.R. Regio-, Peri-, and torqu-oselectivity in hydroxy heptatrienyl cation electrocyclizations: the iso/homonazarov reaction. Chem. Eur. J., 2009, 15, 1944-1956.
29. Tius, M.A.; Busch-Petersen, J.; Yamashita, M. Cross-conjugated cyclopente-none prostaglandins synthesis of 7-10-Chloro-15-deoxy PGA1 ethyl ester. Tetrahedron Lett., 1998, 39, 4219-4222.
30. Iglesias, B.; de Lera A.R.; Rodriguez-Otero, J.; López, S. Torquoselectivity in the cationic cyclopentannelation of (2Z)-Hexa-2,4,5-trienal acetals. Chem. Eur. J., 2000, 6, 4021-4033.
31. Piancatelli, G.; Scettri, A.; Barbadoro, S. A useful preparation of 4-Substituted 5-Hydroxy-3-Oxocyclopentene. Tetrahedron Lett., 1976, 17, 3555-3558.
32. Pinacatelli, G.; Scettri, A.; David, G.; D'Auria, M. A new synthesis of 3-Oxocyclopentenes. Tetrahedron, 1978, 34, 2775-2778.
33. Yin, B.-L.; Wu, Y.-L.; Lai, J.-Q. Novel conversions of furandiols and spi-roacetal enol ethers into Cyclopentenones: implications of the isomerization mechanism of 2-Furylcarbinols into cyclopentenones. Eur. J. Org. Chem., 2009, 2695-2699.
34. Otero, M.P.; Santín, E.P.; Rodríguez-Barrios, F.; Vaz, B.; de Lera, A.R. Selective, potent PPAR agonists with cyclopentenone core structure. Bioorg. Med. Chem. Lett., 2009, 19, 1883-1886.
35. Hammond, G.S. A correlation of reaction rates. J. Am. Chem. Soc., 1955, 77, 334-338.
36. Bell, R.P. The theory of reactions involving proton transfers. Proc. R. Soc. Lond. A., 1936, 154, 414-429.
37. Evans, M.G.; Polanyi, M. Further considerations on the thermodynamics of chemical equilibria and reaction rates. Trans. Faraday Soc., 1936, 32, 1333-1360.
38. For recent reviews on allene oxide cyclizations in enzymes see (a) Jahn, U.; Galano, J.-M; Durand, T. Beyond prostaglandins-chemistry and biology of cyclic oxygenated metabolites formed by free-radical pathways from polyun-saturated fatty acids. Angew. Chem. Int. Ed., 2008, 47, 5894-5955.
39. Hofmann, E.; Pollmann, S. Molecular mechanism of enzymatic allene oxide cyclization in plants. Plant Physiol. Biochem., 2008, 46, 302-308.
40. Hess, B.A. Jr.; Smentek, L.; Brash, A.R.; Cha, J.K. Mechanism of the rear-rangement of vinyl allene oxide to 2-Cyclopenten-1-one. J. Am. Chem. Soc., 1999, 121, 5603-5604.
41. López, C.S.; Faza, O.N.; York, D.M.; de Lera, A.R. Theoretical study of the vinyl allene oxide to cyclopent-2-en-1-one Rearrangement: mechanism, torquoselectivity and solvent effects. J. Org. Chem., 2004, 69, 3635-3644.
42. Dygos, J.H.; Adamek, J.P.; Babiak, K.A.; Behling, J.R.; Medich, J.R.; Ng, J.S.; Wieczorek, J.R. An efficient synthesis of the antisecretory prosta-glandin enisoprost. J. Org. Chem., 1991, 56, 2549-2552.
43. Rodríguez, A.; Nomen, M.; Spur, B.W.; Godfroid, J.-J. An efficient asymmetric synthesis of prostaglandin E1. Eur. J. Org. Chem., 1999, 2655-2662.
44. For a review on furan reactions, see: Piancatelli, G.; D'Auria, M.; D'Onofrio, F. Synthesis of 1,4-dicarbonyl compounds and cyclopentenones from furans. Synthesis, 1994, 867-889.
45. D'Auria, M. A new simple procedure for the isomerization of 2-furylcarbinols to cyclopentenones. Heterocycles, 2000, 52, 185-194.
46. Lewis, K.G.; Mulquiney, C.E. Rearrangements in the furan series. II. The reaction between furfuraldehyde and aromatic amines. Aust. J. Chem., 1979, 32, 1079-1092.
47. Li, S.-W.; Batey, R.A. Mild lanthanide(III) catalyzed formation of 4,5-diaminocyclopent-2-enones from 2-furaldehyde and secondary amines: a domino condensation/ring-opening/electrocyclization process. Chem. Commun., 2007, 3759-3761.
48. For recent reviews on the Nazarov cyclization see: (a) Habermas, K.L.; Denmark, S. E.; Jones, T.K. The nazarov cyclization. Org. React., 1994, 1-158.
49. Tius, M.A. Some new nazarov chemistry. Eur. J. Org. Chem., 2005, 2193-2206.
50. Pellissier, H. Recent developments in the nazarov process. Tetrahedron, 2005, 61, 6479-6517.
51. Frontier, A.J.; Collison, C. The nazarov cyclization in organic synthesis. recent advances. Tetrahedron, 2005, 61, 7577-7606.
52. Smith, D.A.; Ulmer, C.W.II. Effects of substituents in the 3-position on the [2 + 2] pentadienyl cation electrocyclization. J. Org. Chem., 1997, 62, 5110-5115.
53. Smith, D.A.; Ulmer, C.W.II. Identification of multiple transition structures on the potential energy hypersurface for [2 + 2] electro-cyclization of the pentadienyl cation bearing a phosphorus in the 3-position. J. Mol. Graphics, 1995, 13, 283-286.
54. Other non-OR C3 substituents have also been used on occasion. For example, west has recently demonstrated the use of cross-conjugated trienes as pentadienyl cation precursors; see: Rieder, C.J.; Winberg, K.J.; West, F.G. Cyclization of cross-conjugated trienes: the vinylogous nazarov reaction. J. Am. Chem. Soc., 2009, 131, 7504-7505.
55. Esteruelas and co-workers also described an intriguing cyclization involving a system with an osmium directly connected to C3, Bolaño, T.; Castarlenas, R.; Esteruelas, M.A.; Oñate, E. formation of an asymmetric acyclic osmium-dienylcarbene complex. Organometallics, 2008, 27, 6367-6370.
56. Tius, M.A.; Chu C.C.; Nieves-Colberg, R. An imino Nazarov cyclization. Tetrahedron Lett., 2001, 42, 2419-2422.
57. Suárez-Pantiga, S.; Rubio, E.; Alvarez-Rúa, C.; González, J.M.; Intermolecular reaction of internal alkynes and imines: propargyl tosylates as key partners in a gold-catalyzed [4 + 1] unusual cyclization leading to Cyclopent-2-enimines. Org. Lett., 2009, 11, 13-16.
58. Smith, D. A.; Ulmer, C. W. Theoretical studies of the nazarov cychzatlon 1. 1,4-Pentadlen-3-one. Tetrahedron Lett., 1991, 32, 725-728.
59. Frontier has used a variety of heterocycle-containing substrates to generate polarized pentadienyl cations. For a thorough review on polarized Nazarov cyclizations, see reference [37d]. Polarization of the acyclic intermediate results in an increase in the rate of reaction, allowing for the use of milder reaction conditions. For recent examples see: Malona, J.A.; Colbourne, J.M.; Frontier, A.J. A general method for the catalytic nazarov cyclization of het-eroaromatic compounds. Org. Lett., 2006, 8, 5661-5664.
60. He, W.; Herric, I.R.; Atesin, T.A.; Caruana, P.A.; Kellenberger, C.A.; Frontier, A.J. Polarizing the nazarov cyclization: the impact of dienone substitution pattern on reactivity and selectivity. J. Am. Chem. Soc., 2008, 130, 1003-1011.
61. The synthetic utility of these substrates was demonstrated in the syntheses of Merrilactone and Rocaglamide. (He, W.; Huang, J.; Sun, X.; Frontier, A.J. Total Synthesis of (±)-Merrilactone A via Catalytic Nazarov Cyclization. J. Am. Chem. Soc., 2007, 129, 498-499 and reference [6]).
62. Prandi, C.; Deagostino, A.; Venturello, P.; Occhiato, E. G. Stereoselective synthesis of spirocyclic ketones by nazarov reaction. Org. Lett., 2005, 7, 4345-4348.
63. Prandi, C.; Ferrali, A.; Guarna, A.; Venturello, P.; Occhiato, E. G. New synthetic approach to cyclopenta-fused heterocycles based upon a mild nazarov reaction. 2. further studies on the torquoselectivity. J. Org. Chem., 2004, 69, 7705-7709.
64. Occhiato, E. G.; Prandi, C.; Ferrali, A.; Guarna, A.; Venturello, P. New synthetic approach to cyclopenta-fused heterocycles based upon a mild nazarov reaction. J. Org. Chem., 2003, 68, 9728-9741.
65. Cavalli, A.; Masetti, M.; Recanatini, M.; Prandi, C.; Guarna, A.; Occhiato, E. G. Density functional studies on the nazarov reaction involving cyclic systems. Chem. Eur. J., 2006, 12, 2836-2845.
66. Cavalli, A.; Pacetti, A.; Recanatini, M.; Prandi, C.; Scarpi, D.; Occhiato, E. G. Predicting reactivity and stereoselectivity in the nazarov reaction: a combined computational and experimental study. Chem. Eur. J., 2008, 14, 9292-9304.
67. N-Heterocyclic systems similar to 68 had been studied synthetically but not with the methyl ester protecting group.
68. Marcus, A.P.; Lee, A.S.; Davis, R.L.; Tantillo, D.J.; Sarpong, R. Pronounced steric effects of substituents in the nazarov cyclization of aryl dienyl ketones. Angew. Chem. Int. Ed., 2008, 47, 6379-6383.
69. Dieker, J.; Fröhlich, R.; Würthwein, E.-U. Substituted 3-Hydroxypyrroles from 1-Azapenta-1,4-dien-3-ones: the aza-nazarov reaction synthesis and quantum chemical calculations. Eur. J. Org. Chem., 2006, 5339-5365.
70. Ghavtadze, N.; Fröhlich, R.; Würthwein, E.-U. 2H-Pyrrole derivatives from an Aza-Nazarov reaction cascade involving indole as the neutral leaving group. Eur. J. Org. Chem., 2008, 3656-3667.
71. Jalbout, A.F.; Pavanello, M.; Adamowicz, L. The water mediated ring closing in the formose reaction. Int. J. Quantum Chem., 2007, 107, 2024-2031.
72. Olah, G.A.; Klumpp, D.A. Superelectrophiles and their chemistry, John Wiley & Sons: New York, 2007.
73. Olah, G.A. Superelectrophiles. Angew. Chem. Int. Ed. Engl., 1993, 32, 767-788.
74. Olah, G.A.; Klumpp, D.A.; Superelectrophilic solvation. Acc. Chem. Res., 2004, 37, 211-220.
75. Lammertsma, K.; Schleyer, P.v.R.; Schwarz, H. Organic dications: gas phase experiments and theory in concert. Angew. Chem. Int. Ed. Engl., 1989, 28, 1321-1341.
76. Suziki, T.; Ohwada, T.; Shudo, K. Superacid-Catalyzed electrocyclization of diphenylmethyl cations to fluorenes. kinetic and theoretical revisit supporting the involvement of ethylene dications. J. Am. Chem. Soc., 1998, 120, 4629-4637.
77. Braude, E.A.; Forbes, W.F. Polycyclic systems. Part V. A new route to axulenes. J. Chem. Soc., 1953, 2208-2216.
78. deSolms, S.J.; Woltersdorf, O.W., Jr.; Cragoe, E.J., Jr.; Watson, L.S.; Fanelli, G.M., Jr. (Acylary1oxy)acetic Acid Diuretics. 2. (2-Alkyl-2-aryl-1-oxo-5-indany1oxy)acetic Acids. J. Med. Chem. 1978, 21, 437-443.
79. Zhang, Y.; Kindelin, P.J.; DeSchepper, D.; Zheng, C.; Klumpp, D.A. Super-acid-Promoted Reactions of N-Acyliminium Ions: An effective route to substituted 3-Oxo-1,2,3,4-tetrahydroisoquinolines and related products. Synthesis, 2006, 1775-1780.
80. Klumpp, D.A.; Zhang, Y.; O'Connor, M.J.; Esteves, P.M.; de Almeida, L.S. Aza-Nazarov reaction and the role of superelectrophiles. Org. Lett., 2007, 16, 3085-3088.
81. Ghavtadze, N.; Fröhlich, R.; Bergander, K.; Würthwein, E.-U. Superelectrophilic intermediates in the synthesis of novel indenole derivatives via 1,5-Cyclization reactions of 5-Aryl-1-azapenta-1,4-dien-3-ones. Synthesis, 2008, 3397-3406.
82. Rautenstrauch, V. 2-Cyclopentenones from 1-Ethynyl-2-propenyl acetates. J. Org. Chem., 1984, 49, 950-952.
83. Shi, X.; Gorin, D.J.; Toste, F.D. Synthesis of 2-Cyclopentenones by Gold(I)-Catalyzed rautenstrauch rearrangement. J. Am. Chem. Soc., 2005, 127, 5802-5803.
84. Faza, O.N.; López, C.S.; Álverez, R.; de Lera, A.R. Mechanism of the Gold(I)-Catalyzed rautenstrauch rearrangement: a Center-to-Helix-to-Center chirality transfer. J. Am. Chem. Soc., 2006, 128, 2434-2437.
85. Shi, F.-Q.; Li, X.; Xia, Y.; Zhang, L.; Yu, Z. DFT study of the mechanisms of in water Au(I)-Catalyzed Tandem [3,3]-Rearrangement/Nazarov Reaction/[1,2]-Hydrogen Shift of Enynyl Acetates: a proton-transport catalysis strategy in the water-catalyzed [1,2]-Hydrogen Shift. J. Am. Chem. Soc., 2007, 129, 15503-15512.
86. Lemiere, G.; Gandon, V.; Cariou, K.; Fukuyama, T.; Dhiman, A.; Fensterbank, L.; Malacria, M. Tandem Gold(I)-Catalyzed Cyclization/Electrophilic cyclopropanation of vinyl allenes. Org. Lett., 2007, 9, 2207-2209.
87. Gandon, A.; Lemiere, G.; Hours, A.; Fensterbank, L.; Malacria, M. The role of bent acyclic allene gold complexes in Axis-to-Center chirality transfers. Angew. Chem. Int. Ed., 2008, 47, 7534-7538.
88. Lemiere, G.; Gandon, V.; Cariou, K.; Hours, A.; Fukuyama, T.; Dhimane, A.; Fensterbank, L.; Malacria, M. Generation and trapping of cyclopentenylidene gold species: four pathways to polycyclic compounds. J. Am. Chem. Soc., 2009, 131, 2993-3006.
89. Shoppee, C.W.; Henderson, G.N.; Electrocyclisation of the 1,5-Diphenylpenta-1,4-dienyl Anion. J. Chem. Soc., Chem. Commun., 1974, 561-562.
90. Lopez, C.S.; Faza, O.N.; Cossio, F.P.; York, D.M.; de Lera, A.R. Ellipticity: A convenient tool to characterize electrocyclic reactions. Chem. Eur. J., 2005, 11, 1734-1738.
91. Ogorodnikova, N.A.; Mitnik, D.M. Ab initio study of the additivity concept applied for the effects of one substituent within cyclic compounds. J. Mol. Struct., 2001, 538, 267-285.
92. Yadav, V.K.; Kumar, N.V.; 2,3-Heteroaromatic ring-fused cyclohex-anones via heteroaromatic homo-Nazarov cyclization of donor-acceptor substituted cyclopropanes. Chem. Commun., 2008, 3774-3776.
93. De Simone, F.; Andres, J.; Torosantucci, R.; Waser, J. catalytic formal Homo-Nazarov Cyclization. Org. Lett., 2009, 11, 1023-1026.