Complex thermal behavior of 11-cis-retinal, the ligand of the visual pigments

Journal of Organic Chemistry

Volumn 74, Issue 3, 2009, Pages 1007-1013

  López, Carlos Silva ^a   Álvarez, Rosana ^a   Domínguez, Marta ^a   Faza, Olalla Nieto ^a   De Lera, Angel R ^a  

^a UNIVERSITY OF VIGO   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

CIS-DOUBLE BONDS; COMPUTATIONAL RESULTS; DENSITY FUNCTIONAL THEORY METHODS; DIRADICAL; ELECTROCYCLIC REACTIONS; INTERNAL ROTATIONS; ISOTOPOLOGUES; PERICYCLIC REACTIONS; PRODUCT COMPOSITIONS; SIGMATROPIC SHIFTS; THERMAL BEHAVIORS; TRANS-ISOMERS; TRANSITION STATE; VISUAL PIGMENTS;

CHEMICAL BONDS; DENSITY FUNCTIONAL THEORY; DEUTERIUM; ISOMERS; OPHTHALMOLOGY;

ALDEHYDES;

11 CIS RETINAL; DEUTERIUM; RETINAL; VISUAL PIGMENT;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; DENSITY FUNCTIONAL THEORY; HEATING; ISOMERIZATION;

HOT TEMPERATURE; ISOMERISM; KINETICS; LIGANDS; MAGNETIC RESONANCE SPECTROSCOPY; MODELS, MOLECULAR; MOLECULAR CONFORMATION; RETINALDEHYDE; RHODOPSIN; THERMODYNAMICS;

EID: 64549123972     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo801899k     Document Type: Article

References (51)

1. De Grip, W. J.; Rothschild, K. J. In Molecular Mechanisms of Visual Transduction; Stavenga, D. G., De Grip, W. J., Pugh, E. N., Jr., Eds.; Elsevier: Amsterdam, 2000; p 1.
2. (a) Yan, E. C. Y.; Ganim, Z.; Kazmi, M. A.; Chang, B. S. W.; Sakmar, T. P.; Mathies, R. A. Biochemistry 2004, 43, 10867-10876.
3. (b) Kukura, P.; McCamant, D. W.; Yoon, S.; Wandschneider, D. B.; Mathies, R. A. Science 2005, 310, 1006-1009.
4. (a) Rando, R. R. Chem. Rev. 2001, 101, 1881-1896.
5. (b) Fishkin, N.; Berova, N.; Nakanishi, K. Chem. Rec. 2004, 4, 120-135.
6. (a) McBee, J. K.; Palczewski, K.; Baehr, W.; Pepperberg, D. R. Prog. Ret. Eye Res. 2001, 20, 469-529.
7. (b) Ridge, K. D.; Palczewski, K. J. Biol. Chem. 2007, 282, 9297-9301.
8. Barlow, R.; Birge, R.; Kaplan, E.; Tallent, J. Nature 1993, 366, 64-66.
9. Valle, L. J. D.; Ramon, E.; Bosch, L.; Manyosa, J.; Garriga, P. Cell. Mol. Life Sci. 2003, 60, 2532-2537, The authors pointed out that the thermal instability of rhodopsin at 55 °C may suggest a connection between some retinal diseases and mutations in the apoprotein that mimic the destabilizing effect of the temperature.
10. Hubbard, R. J. Biol. Chem. 1966, 241, 1814-1818.
11. Liu, R. S. H.; Asato, A. E. Tetrahedron 1984, 40, 1931-1969.
12. Gascon, J. A.; Sproviero, E. M.; Batista, V. S. Acc. Chem. Res. 2006, 39, 184-193.
13. (a) Sperling, W.; Carl, P.; Rafferty, Ch. N.; Dencher, N. A. Biophys. Struct. Mech. 1977, 3, 79-94.
14. (b) Rando, R. R.; Chang, A. J. Am. Chem. Soc. 1983, 105, 2879-2882.
15. Bonacic-Koutecky, V.; Koutecky, J.; Michl, J. Angew. Chem., Int. Ed. 1987, 26, 170-189.
16. Some thermal experiments showed that 13-cis-retinal 2 produced ca. 10% all-trans-retinal 3 upon prolonged heating even in carefully deactivated glassware. But under these conditions, the 13-cis 2 and all-trans 3 ratio never reach the ca. 65:35 ratio found in the thermal isomerization of 11-cis-retinal 1.
17. In the restricted environment of the opsin protein (as has been found in bacteriorhodopsin, the proton pumping device of halobacteria, which uses a protonated Schiff base of all-trans-retinal as chromophore) or in the solid state, retinoids have been reported to undergo double-bond isomerizations via concerted motions (hula twist and bicycle pedal); see:
18. (a) Liu, R. S. H.; Browne, D. T. Acc. Chem. Res. 1986, 19, 42-48.
19. (b) Baudry, J.; Crouzy, S.; Roux, B.; Smith, J. C. Biophys. J. 1999, 76, 1909-1917. The same studies accept that, in solution, the most favored isomerization mechanism is the sequential pathway, where each double-bond rotation occurs as a single and independent step. We thoroughly explored this possibility and reached similar conclusions: the concerted isomer-ization about C11-C12 and C13-C14 lies very high in energy (ca. 48.6 kcal/ mol) and the stationary point associated with such a transformation was found to be a second-order saddle point (see the Supporting Information). Other theoretical studies rule out the bicycle pedal motion of the photoexcited chromophore, which moreover appears to restrict its movement to the C10-C11-C12-C13 fragment (a so-called "photochemical hot spot"), whereas the rest of the molecule begins to rotate only upon relaxation to the ground state; see:
20. (c) Weingart, O. J. Am. Chem. Soc. 2007, 129, 10618-10619.
21. (a) Okamura, W. H.; de Lera, A. R. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Paquette, L. A.,Volume Ed.; Pergamon Press: London, 1991; Vol. 5, Chapter 6.2, pp 699-750.
22. (b) Marvell, E. N. Thermal Electrocyclic Reactions; Academic Press: New York, 1980. (c) Burnier, J. S.;Jorgensen, W. L. J. Org. Chem. 1984, 49, 3001-3020.
23. (a) Sakai, N.; Decatur, J.; Nakanishi, K.; Eldred, G. E. J. Am. Chem. Soc. 1996, 115, 1559-1560.
24. (b) Parish, C. A.; Hashimoto, M.; Nakanishi, K.; Dillon, J.; Sparrow, J. Proc. Natl. Acad. Sci. U.S.A. 1998, 95, 14609-14613.
25. (c) Ben-Shabat, S.; Parish, C. A.; Hashimoto, M.; Liu, J.; Nakanishi, K.; Sparrow, J. R. Bioorg. Med. Chem. Lett. 2001, 11, 1533-1540.
26. (d) Fishkin, N.; Jang, Y.-P.; Itagaki, Y.; Sparrow, J. R.; Nakanishi, K. Org. Biomol. Chem. 2003, 1, 1101-1105. For the synthesis of A2E model systems involving an aza-6n-electrocyclization of Schiff bases, see:
27. (e) Tanaka, K.; Katsumura, S. Org. Lett. 2000, 2, 373-375.
28. A dimerization mode of retinal alternative to that leading to A2E involves also a pericyclic reaction and affords a pigment epithelial cell fluorophore: Fishkin, N.; Sparrow, J. R.; Allikmets, R.; Nakanishi, K. Proc. Natl. Acad. SciU.S.A. 2005, 102, 7091-7096.
29. (a) Okamura, W. H.; Lera, A. R. D.; Reischl, W. J. Am. Chem. Soc. 1988, 110, 4462-4464. (b) de Lera, A.; Reischl, W.; Okamura, W. J. Am. Chem. Soc. 1989, 111, 4051-4063.
30. The ring-closure activation energy computed (49.77 kcal/mol) is in good agreement with previous computations of analogous systems at the MP4SDTQ/
31. 6-31G(d) level; see: Yu, H.; Chan, W. T.; Goddard, J. D. J. Am. Chem. Soc. 1990, 112, 7529-7537.
32. The mechanism of isomerization of di-cis-dienals and dienones to the monocis isomers through formation of a-pyrans had been previously studied by Kluge and Lillya: (a) Kluge, A. F.; Lillya, C. P. J. Org. Chem. 1971, 36, 1977-1988.
33. (b) Kluge, A. F.; Lillya, C. P. J. Org. Chem. 1971, 36, 1988-1995.
34. (a) 11,13-Di-cis-retinal was first shown to convert to 13-cis-retinal by Wald et al. in 1955: Wald, G.; Hubbard, R.; Brown, P. K.; Oroshnik, W. Proc. Natl. Acad. Sci. U.S.A. 1955, 41, 438-451.
35. (b) The isomerization of the 11-cis double bond of 11,13-di-cis-retinal and 9,11,13-tri-cis-retinal was studied by Okamura: Knudsen, C. G.; Chandraratna, R. A. S.; Walkeapaa, L. P.; Chauhan, Y. S.; Carey, S. C.; Cooper, T. M.; Birge, R. R.; Okamura, W. H. J. Am. Chem. Soc. 1983, 105, 1626-1631.
36. (c) In addition, Liu described the thermal rearrangement of the four labile isomers of retinal (11,13-di-cis-, 7,11,13-tri-cis-, 9,11,13-tri-cis-, and all-cis-retinal) presumably occurring via consecutive 6ne--heteroelectrocyclization reactions and determined the kinetic parameters of these processes: Zhu, Y.; Ganapathy, S.; Liu, R. S. H. J. Org. Chem. 1992, 57, 1110-1113.
37. Dolbier, W. R., Jr.; Koroniak, H.; Houk, K. N.; Sheu, C. Acc. Chem. Res. 1996, 29, 471-477.
38. For the first demonstration of the antarafacial nature of a [1,7]-H hydrogen shift in the previtamin D series, see: (a) Hoeger, C. A.; Okamura, W. H. J. Am. Chem. Soc. 1985, 107, 268-269.
39. (b) Hoeger, C. A.; Johnston, A. D.; Okamura, W. H. J. Am. Chem. Soc. 1987, 109, 4690-4698.
40. Using the Maxwell-Boltzmann distribution.
41. Isotope effects (kH/kD of about 6) have been measured in the [1,7]-H sigmatropic shift of the previtamin D system:
42. (a) Okamura, W. H.; Hoeger, C. A.; Miller, K. J.; Reischl, W. J. Am. Chem. Soc. 1988,110, 973-974.
43. (b) For simple trienes, the values are lower; see: Okamura, W. H.; Elnagar, H. Y.; Ruther, M.; Dobreff, S. J. Org. Chem. 1993, 58, 600-610.
44. all-trans-Retinal-14,19,19-d3 is formed by direct rotation about the C11-C12doublebondin11-cis-retinal-14,19,19-d3which, inturn, isformedvia[1,7]-H sigmatropic shift driven H/D scrambling from the parent 11-cis-retinal-19,19,19-d3 (see Figure 5).
45. Sreeruttun, R. K.; Ramasami, P.; Wannere, C. S.; Paul, A.; von R. Schleyer, P.; Schaeffer, H F., III. J. Org. Chem. 2005, 70, 8676-8686.
46. Francesch, A.; Alvarez, R.; Lopez, S.; de Lera, A. R. J. Org. Chem. 1997, 62, 310-319.
47. (a) Becke, A. D. Phys. Rev.A1988, 38, 3098-3100.
48. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
49. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev.B.1988, 37, 785-789.
50. Foresman, J. B. Frisch, E. Exploring Chemistry with Electronic Structure Methods, 2nd ed.; Gaussian, Inc.: Pittsburgh, PA, 1996.
51. Bauernschmitt, R.; Ahlrichs, R. J. Chem. Phys. 1996, 104, 9047-9052.