Dynamically Complex [6+4] and [4+2] Cycloadditions in the Biosynthesis of Spinosyn A

Journal of the American Chemical Society

Volumn 138, Issue 11, 2016, Pages 3631-3634

  Patel, Ashay ^a   Chen, Zhuo ^b   Yang, Zhongyue ^a   Gutiérrez, Osvaldo ^a,d   Liu, Hung Wen ^c   Houk, K N ^a   Singleton, Daniel A ^b  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b TEXAS A AND M UNIVERSITY   (United States)

^c University of Texas at Austin   (United States)

^d UNIVERSITY OF PENNSYLVANIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BIOCHEMISTRY; BIOSYNTHESIS; ENZYMES; POTENTIAL ENERGY; QUANTUM CHEMISTRY; QUANTUM THEORY;

BOND FORMATION; COPE REARRANGEMENT; CYCLOADDITIONS; CYCLOADDUCTS; DIELS-ALDER REACTION; DYNAMICAL EFFECTS; QUANTUM MECHANICAL COMPUTATIONS; TRANSITION STATE;

CYCLOADDITION;

SPINOSYN A; MACROLIDE;

ARTICLE; BIOSYNTHESIS; CHEMICAL BOND; CHEMICAL STRUCTURE; COMPLEX FORMATION; COPE REARRANGEMENT; CYCLOADDITION; DIELS ALDER REACTION; ENZYME MECHANISM; QUANTUM MECHANICS; SIMULATION; SURFACE PROPERTY; CHEMISTRY; METABOLISM; MOLECULAR MODEL; QUANTUM THEORY; THERMODYNAMICS;

CYCLOADDITION REACTION; MACROLIDES; MODELS, MOLECULAR; QUANTUM THEORY; THERMODYNAMICS;

EID: 84962109823     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/jacs.6b00017     Document Type: Article

References (40)

1. Stocking, E. M.; Williams, R. M. Angew. Chem., Int. Ed. 2003, 42, 3078 10.1002/anie.200200534
2. Oikawa, H.; Tokiwano, T. Nat. Prod. Rep. 2004, 21, 321 10.1039/b305068h
3. Kelly, W. L. Org. Biomol. Chem. 2008, 6, 4483 10.1039/b814552k
4. Kim, H. J.; Ruszczycky, M. W.; Liu, H.-w. Curr. Opin. Chem. Biol. 2012, 16, 124 10.1016/j.cbpa.2011.12.017
5. Klas, K.; Tsukamoto, S.; Sherman, D. H.; Williams, R. M. J. Org. Chem. 2015, 80, 11672 10.1021/acs.joc.5b01951
6. Laschat, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 289 10.1002/anie.199602891
7. Diels, O.; Alder, K. Liebigs Ann. Chem. 1928, 460, 98 10.1002/jlac.19284600106
8. Auclair, K.; Sutherland, A.; Kennedy, J.; Witter, D. J.; Van den Heever, J. P.; Hutchinson, C. H.; Vederas, J. C. J. Am. Chem. Soc. 2000, 122, 11519 10.1021/ja003216+
9. Kennedy, J.; Auclair, K.; Kedrew, S. G.; Park, C.; Vederas, J. C.; Hutchinson, C. H. Science 1999, 284, 1368 10.1126/science.284.5418.1368
10. Ma, S. M.; Li, J. W.-H.; Choi, J. W.; Zhou, H.; Lee, K. K. M.; Moorthie, V. A.; Xie, X.; Kealey, J. T.; Da Silva, N. A.; Vederas, J. C.; Tang, Y. Science 2009, 326, 589 10.1126/science.1175602
11. Kim, H. J.; Ruszczycky, M. W.; Choi, S.-H.; Liu, Y.-N.; Liu, H.-w. Nature 2011, 473, 109 10.1038/nature09981
12. Hashimoto, T.; Hashimoto, J.; Teruya, K.; Hirano, T.; Shin-ya, K.; Ikeda, H.; Liu, H.-w.; Nishiyama, M.; Kuzuyama, T. J. Am. Chem. Soc. 2015, 137, 572 10.1021/ja510711x
13. Sato, M.; Yagishita, F.; Mino, T.; Uchiyama, N.; Patel, A.; Chooi, Y.-H.; Goda, Y.; Xu, W.; Noguchi, H.; Yamamoto, T.; Hotta, K.; Houk, K. N.; Tang, Y.; Watanabe, K. ChemBioChem 2015, 16, 2294 10.1002/cbic.201500386
14. Woodward, R. B. J. Am. Chem. Soc. 1942, 64, 3058 10.1021/ja01264a521
15. Houk, K. N.; González, J.; Li, Y. Acc. Chem. Res. 1995, 28, 81 10.1021/ar00050a004
16. Sauer, J.; Sustmann, R. Angew. Chem., Int. Ed. Engl. 1980, 19, 779 10.1002/anie.198007791
17. Hess, B. A. J.; Smentek, L. Org. Biomol. Chem. 2012, 10, 7503 10.1039/c2ob25827g
18. Black, K.; Liu, P.; Xu, L.; Doubleday, C.; Houk, K. N. Proc. Natl. Acad. Sci. U. S. A. 2012, 109, 12860 10.1073/pnas.1209316109
19. Pham, H. V.; Houk, K. N. J. Org. Chem. 2014, 79, 8968 10.1021/jo502041f
20. Quadrelli, P.; Romano, S.; Toma, L.; Caramella, P. J. Org. Chem. 2003, 68, 6035 10.1021/jo034401j
21. Thomas, J. B.; Waas, J. R.; Harmata, M.; Singleton, D. A. J. Am. Chem. Soc. 2008, 130, 14544 10.1021/ja802577v
22. Wang, Z.; Hirschi, J. S.; Singleton, D. A. Angew. Chem., Int. Ed. 2009, 48, 9156 10.1002/anie.200903293
23. Caramella, P.; Quadrelli, P.; Toma, L. J. Am. Chem. Soc. 2002, 124, 1130 10.1021/ja016622h
24. Hoffmann, R.; Woodward, R. B. J. Am. Chem. Soc. 1965, 87, 2046 10.1021/ja01087a034
25. Woodward, R. B.; Hoffmann, R. Angew. Chem., Int. Ed. Engl. 1969, 8, 781 10.1002/anie.196907811
26. Cookson, R. C.; Drake, B. V.; Hudec, J.; Morrison, A. Chem. Commun. 1996, 15 10.1039/c19660000015
27. Houk, K. N.; Woodward, R. B. J. Am. Chem. Soc. 1970, 92, 4145 10.1021/ja00716a074
28. Mukherjee, D.; Dunn, L. C.; Houk, K. N. J. Am. Chem. Soc. 1979, 101, 251 10.1021/ja00495a058
29. Garst, M. E.; Roberts, V. A.; Prussin, C. J. Org. Chem. 1982, 47, 3969 10.1021/jo00141a032
30. Isakovic, L.; Ashenhurst, J. A.; Gleason, J. L. Org. Lett. 2001, 3, 4189 10.1021/ol016814h
31. Rigby, J. H.; Fleming, M. Tetrahedron Lett. 2002, 43, 8643 10.1016/S0040-4039(02)02159-7
32. Sun, L.; Hase, W. L. Rev. Comput. Chem. 2003, 19, 79 10.1002/0471466638.ch3
33. Lourderaj, U.; Park, K.; Hase, W. L. Int. Rev. Phys. Chem. 2008, 27, 361 10.1080/01442350802045446
34. The resulting variational transition states are dynamical bottlenecks and correspond to maxima in the free energy along the MEP from reactant to product. Truhlar, D. G.; Garrett, B. C. Acc. Chem. Res. 1980, 13, 440 10.1021/ar50156a002
35. Doubleday, C. J. Phys. Chem. 1996, 100, 3520 10.1021/jp9528471
36. Baldwin, J. E.; Fleming, M. Fortsch. Chem. Forschung 1970, 15, 281 10.1007/BFb0050819
37. Firestone, R. A. J. Org. Chem. 1968, 33, 2285 10.1021/jo01270a023
38. Hong, Y. J.; Tantillo, D. J. Nat. Chem. 2014, 6, 104 10.1038/nchem.1843
39. Wang, T.; Hoye, T. R. Nat. Chem. 2015, 7, 641 10.1038/nchem.2281
40. Yu, P.; Patel, A.; Houk, K. N. J. Am. Chem. Soc. 2015, 137, 13518 10.1021/jacs.5b06656