Computational studies on the cyclizations of enediynes, enyne-allenes, and related polyunsaturated systems

Accounts of Chemical Research

Volumn 38, Issue 1, 2005, Pages 29-37

  Schreiner, Peter R ^a,b,c,d   Navarro Vazquez, Armando ^a,e   Prall, Matthias ^d,f  

^a JUSTUS LIEBIG UNIVERSITY   (Germany)

^b UNIVERSITY OF GEORGIA   (United States)

^c UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

^d UNIVERSITY OF GÖTTINGEN   (Germany)

^e UNIVERSITY OF SANTIAGO DE COMPOSTELA   (Spain)

^f UNIVERSITY OF KASSEL   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; ALKYNE; ALLENE DERIVATIVE; FUNCTIONAL GROUP; RADICAL;

ARTICLE; CHEMICAL REACTION; CYCLIZATION; GENERALIZED GRADIENT APPROXIMATION; PREDICTION; QUANTUM CHEMISTRY; SINGLE POINT ENERGY COUPLED CLUSTER COMPUTATION; TECHNIQUE; UNRESTRICTED BROKEN SPIN SYMMETRY APPROACH;

ALKENES; ALKYNES; COMPUTATIONAL BIOLOGY; CYCLIZATION; MOLECULAR STRUCTURE; POLYMERS; THERMODYNAMICS;

EID: 12344289470     PISSN: 00014842     EISSN: None     Source Type: Journal    
DOI: 10.1021/ar020270h     Document Type: Article

References (62)

1. (a) Jones, R. R.; Bergman, R. G. p-Benzyne. Generation as an Intermediate in a Thermal Isomerization reaction and trapping evidence for the 1,4-Benzenediyl structure. J. Am. Chem. Soc. 1972, 94, 660-661.
2. (b) Darby, N.; Kim, C. U.; Salaun, J. A.; Shelton, K. W.; Takada, S.; Masamune, S. The 1,5-didehydro[10]annulene system. Chem. Commun. 1971, 1516-1517.
3. (c) Bergman, R. G. Reactive 1,4-dehydroaromatics. Acc. Chem. Res. 1973, 6, 25-31.
4. Grissom, J. W.; Gunawardena, G. U.; Klinberg, D.; Huang, D. The chemistry of enediynes, enyne allenes and related compounds. Tetrahedron 1996, 52, 6453-6518.
5. (a) Perpall, M. W.; Perera, K. P. U.; DiMaio, J.; Ballato, J.; Foulger, S. H.; Smith, D. W., Jr. Novel Network Polymer for Templated Carbon Photonic Crystal Structures. Langmuir 2003, 19, 7153-7156.
6. (b) Schreiner, P. R.; Prall, M.; Lutz, V. Fulvenes from Enediynes: Regioselective Electrophilic Domino and Tandem Cyclizations of Enynes and Oligoynes. Angew. Chem., Int. Ed. 2003, 42, 5757-5760.
7. Borders, D. B.; Doyle, T. W. Enediyne Antibotics as Antitumor Agents; Marcel Dekker: New York, 1995.
8. (a) Myers, A. G.; Kuo, E. Y.; Finney, N. S. Thermal Generation of α,3-Dehydrotoluene from (Z)-1,2,4-Heptatrien-6-yne. J. Am. Chem. Soc. 1989, 111, 8057-8059.
9. (b) Myers, A. G.; Dragovich, P. S.; Kuo, E. Y. Studies on the Thermal Generation and Reactivity of a Class of (σ,π)-1,4-biradicals. J. Am. Chem. Soc. 1992, 114, 9369-9386.
10. (c) Nagata, R.; Yamanaka, H.; Murahashi, E.; Saito, I. DNA cleavage by acyclic enyne-allene systems related to neocarzinostatin and esperamicin-calicheamicin. Tetrahedron Lett. 1990, 31, 2907-2910.
11. (a) Schmittel, M.; Strittmatter, M.; Kiau, S. Switching from the Myers reaction to a new thermal cyclization mode in enyne-allenes. Tetrahedron Lett. 1995, 36, 4975-4978.
12. 6-cyclization and DNA strand cleavage. Tetrahedron Lett. 1996, 37, 7691-7694.
13. Computational chemists or theoreticians often incorrectly use the term "predict" in place of "describe" or "compute". This was printed out in 1967 in a footnote by Paul v. R. Schleyer: "In the current literature, the word "predict" is often used rather curiously as a synonym for "explain" or "rationalize" rather than "foretell, tell beforehand, prophecy," as favored by dictionaries. It is impossible to "predict" something when the fact is known beforehand. An aphorism, original source unknown, stresses this point: "Predictions are risky, especially if they deal with the future". True quantitative predictions, in organic chemistry at least, are quite rare." Gleicher, G. J.; Schleyer, P. v. R. Conformational analysis of bridgehead carbonium ions. J. Am. Chem. Soc. 1967, 89, 582-593.
14. Navarro-Vázquez, A.; Prall, M.; Schreiner, P. R. Cope Reaction Families: To Be or Not to Be a Biradical. Org. Lett. 2004, 6, 2981-2984.
15. Houk, K. N.; Li, Y.; Evanseck, J. D. Transition structures of Hydrocarbon Pericyclic Reactions. Angew. Chem., Int. Ed. Engl. 1992, 31, 682-708.
16. Hopf, H. Classics in Hydrocarbon Chemistry, Wiley-VCH: Weinheim, Germany, 2000.
17. Roth, W. R.; Hopf, H.; Horn, C. Energy well of diradicals. V. 1,3,5-Cyclohexatriene-1,4-diyl and 2,4-cyclohexadiene-1,4-diyl. Chem. Ber. 1994, 127, 1765-1769.
18. Wenthold, P. G.; Squires, R. R.; Lineberger, W. C. Ultraviolet Photoelectron Spectroscopy of the o-, m-, and p-Benzyne Negative Ions. Electron Affinities and Singlet-Triplet Splittings for o-, m-, and p-Benzyne J. Am. Chem. Soc. 1998, 120, 5279-5290.
19. Grafenstein, J.; Hjerpe, A. M.; Kraka, E.; Cremer, D. An Accurate Description of the Bergman Reaction Using Restricted and Unrestricted DFT: Stability Text, Spin Density and On-Top Pair Density. J. Phys. Chem. A 2000, 104, 1748-1761.
20. Cramer, C. J.; Squires, R. R. Quantum Chemical Characterization of the Cyclization of the Neocarzinostatin Chromophore to the 1,5-Didehydroindene Biradical. Org. Lett. 1999, 1, 215-218.
21. Wenthold, P. G.; Wierschke, S. G.; Nash, J. J.; Squires, R. R. α,3-Dehydrotoluene: Experimental and Theoretical Evidence for a Singlet Ground State. J. Am. Chem. Soc. 1993, 115, 12611-12612.
22. 6 ("Schmittel") Cyclizations of Parent and Monocyclic Enyne-Allenes; Challenges to Chemistry and Computation. J. Am. Chem. Soc. 1999, 121, 8615-8627.
23. All single configurations are avoided here by symmetry.
24. de Visser, S. P.; Filatov, M.; Schreiner, P. R.; Shaik, S. A REKS Assessment of the Face-Diagonal Bond in 1,3-Didehydrocubane and a Comparison with Benzyne Biradicals. Eur. J. Org. Chem. 2003, 4199-4204.
25. Gräfenstein, J.; Kraka, E.; Filatov, M.; Cremer, D. Can Unrestricted Density Functional-Theory Describe Open Shell Singlet Biradicals? Int. J. Mol. Sci. 2002, 3, 360-394.
26. In ref 19, Kraka and co-workers distinguish between the normal HOMO-LUMO mixing (UBS) procedure and orbital permutation, which they called PO-UDFT.
27. Hanrath, M.; Engels, B. New algorithms for an individually selecting MR-CI program. Chem. Phys. 1997, 225, 197-202.
28. Andersson, K.; Malmqvist, P.-Å.; Roos, B. O. Second-order perturbation theory with a complete active space self-consistent field reference function. J. Chem. Phys. 1992, 96, 1218-1226.
29. Lindh, R.; Persson, B. J. Ab Initio Study of the Bergman Reaction: The Autoaromatization of Hex-3-ene-1,5-dyine. J. Am. Chem. Soc. 1994, 116, 4963-4969.
30. Andersson, K. Different forms of the zeroth-order Hamiltonian in second-order perturbation theory with a complete active space self-consistent field reference function. Theor. Chim. Acta 1995, 91, 31-46.
31. McDouall, J. J. W.; Peasley, K.; Robb, M. A. A simple MC-SCF perturbation theory: orthogonal valence bond Moeller-Plesset 2(OVB MP2). Chem. Phys. Lett. 1988, 148, 183-189.
32. Lindh, R.; Lee, T. J.; Bernhardsson, A.; Persson, B. J.; Karlström, G. Extended ab Initio and Theoretical Themodynamics Studies of the Bergman Reaction and the Energy Splitting of the Singlet o-, m-, and p-Benzynes. J. Am. Chem. Soc. 1995, 117, 7186-7194.
33. Hoffner, J.; Schottelius, M. J.; Feichtinger, D.; Chen, P. Chemistry of the 2,5-Didehydropyridine Biradical: Computational, Kinetic, and Trapping Studies toward Drug Design. J. Am. Chem. Soc. 1998, 120, 376-385.
34. Nakano, H. Quasidegenerate perturbation theory with multiconfigurational self-consistent-field reference functions. J. Chem. Phys. 1993, 99, 7983-7992.
35. Koseki, S.; Fujimura, Y.; Hiramara, M. Benzannelation Effect in Enedyine Cycloaromatization: An ab Initio Molecular Orbital Study. J. Phys. Chem. A 1999, 103, 7672-7675.
36. 6 Cyclization. J. Am. Chem. Soc. 1998, 120, 6356-6361.
37. 6 Cyclization. Angew. Chem., Int. Ed. 1998, 37, 1960-1963.
38. Galbraith, J. M.; Schreiner, P. R.; Harris, N.; Wei, W.; wittkopp, A.; Shaik, S. A Valence Bond Study of the Bergman Cyclization: Geometric Features, Resonance Energy, and Nucleus-Independent Chemical Shift (NICS) Values. Chem-Eur. J. 2000, 6, 1446-1454.
39. Cramer, C. J. Bergman, Aza-Bergman and Protonated Aza-Bergman Cyclizations and Intermediate 2,5-Arynes: Chemistry and Challenges to Computation. J. Am. Chem. Soc. 1998, 120, 6261-6269.
40. Handy, N. C.; Pople, J. A.; Head-Gordon, M.; Raghavachari, K.; Trucks, G. W. Size-consistent Brueckner theory limited to double substitutions. Chem. Phys. Lett. 1989, 164, 185-192.
41. Chen, W.-C.; Zou, J.-W.; Yu, C.-H. Density Functional Study of the Ring Effect on the Myers-Saito Cyclization and a Comparison with the Bergman Cyclization. J. Org. Chem. 2003, 68, 3663-3672.
42. 1 point group allowing some mixing of HOMO and LUMO A′ and A″ orbitals.
43. Crawford, T. D.; Kraka, E.; Stanton, J. F.; Cremer, D. Problematic p-benzyne: Orbital instabilities, biradical character, and broken symmetry. J. Chem. Phys. 2001, 114, 10638-10650.
44. Chen, W.-C.; Chang, N.-y.; Yu, C.-h. Density Functional Study of Bergman Cyclization of Enedyines. J. Phys. Chem. A 1998, 102, 2584-2593.
45. Koch, W.; Holthausen, M. C. A Chemist's Guide to Density Functional Theory, Wiley-VCH: Weinheim, Germany, 2000.
46. Although RDFT description of transition state 2 was stable at all levels, the stability of restricted calculations on transition states for these cyclizations should be always checked since very often RDFT and UBS-DFT descriptions are very close energetically.
47. (a) Cremer, D.; Filatov, M.; Polo, V.; Kraka, E.; Shaik, S. Implicit and Explicit Coverage of Multireference Effects by Density Functional Theory. Int. J. Mol. Sci. 2002, 3, 604-638.
48. (b) Polo, V.; Kraka, E.; Cremer, D. Some thoughts about the stability and reliability of commonly used exchange-correlation functionals - coverage of dynamic and nondynamic correlation effects. Theor. Chem. Acc. 2002, 107, 291-303.
49. Hess, B. A., Jr. Do Bicyclic Forms of m- and p-Benzyne Exist? Eur. J. Org. Chem. 2001, 2185-2189.
50. Winkler, M.; Sander, W. The Structure of m-Benzyne Revisited - A Close Look into σ-bond Formation. J. Phys. Chem. A 2001, 105, 10422-10432.
51. Sander, W.; Exner, M.; Winkler, M.; Balster, A.; Hjerpe, A.; Kraka, E.; Cremer, D. Vibrational Spectrum of m-Benzyne: A Matrix Isolation and Computational Study. J. Am. Chem. Soc. 2002, 124, 13072-13079.
52. (a) Filatov, M.; Shaik, S. A spin-restricted ensemble-referenced Kohn-Sham method and its application to diradicaloid situations. Chem. Phys. Lett. 1999, 304, 429-437.
53. (b) de Visser, S. P.; Filatov, M.; Shaik, S. REKS calculations on ortho-, meta- and para-benzyne. Phys. Chem. Chem. Phys. 2000, 2, 5046-5048.
54. (c) de Visser, S. P.; Filatov, M.; Shaik, S. Myers-Saito and Schmittel Cyclization of hepta-1,2,4-triene-6-yne: A theoretical REKS study. Phys. Chem. Chem. Phys. 2001, 3, 1242-1245.
55. Prall, M.; Wittkopp, A.; Schreiner, P. R. Can Fulvenes Form from Enedyines? A Systematic High-Level Computational Study on Parent and Benzannelated Enedyine and Enyne-Allene Cyclizations. J. Phys. Chem. A 2001, 105, 9265-9274.
56. Kraka, E.; Cremer, D. Computer Design of Anticancer Drugs. A New Enedyine Warhead. J. Am. Chem. Soc. 2000, 122, 8245-8264.
57. Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao, H.; von Eikema Hommes, N. J. R. Nucleus-Independent Chemical Shifts (NICS): A Simple and Efficient Aromaticity Probe. J. Am. Chem. Soc. 1996, 118, 6317-6318.
58. Stahl, F.; Moran, D.; Schleyer, P. v. R.; Prall, M.; Schreiner, P. R. Aromaticity of the Bergman, Myers-Saito, Schmittel and Directly Related Cyclizations of Enedyines. J. Org. Chem. 2002, 67, 1453-1461.
59. Alabugin, I. V.; Manoharan, M. Reactant Destabilization in the Bergman Cyclization and Rational Design of Light- and pH-Activated Enediynes. J. Phys. Chem. A 2003, 107, 3363-3371.
60. Prall, M.; Wittkopp, A.; Fokin, A. A.; Schreiner, P. R. Substituent effects on the Bergman Cyclization of (Z)-1,5-Hexadiyne-3-enes: A Systematic Computational Study. J. Comput. Chem. 2001, 22, 1605-1614.
61. Kawatkar, S.; Schreiner, P. R. Cycloaromatization of 1,4-Pentadiynes. A viable possibility? Org. Lett. 2002, 4, 3643-3646.
62. Bui, B. H.; Schreiner, P. R. Beyond Schmittel and Myers-Saito Cyclizations: Rearrangements of 4-Heteroatom-1,2-hexa-diene-5-ynes. Org. Lett. 2003, 5, 4871-4874.