Citation: Mu Weihua, Ma Yao, Fang Decai, Wang Rong, Zhang Haina. Computational Insights into the Diels-Alder-alike Reactions of 1-Iodo-2-Lithio-o-Carborane with Fulvenes[J]. Acta Chimica Sinica, ;2018, 76(1): 55-61. doi: 10.6023/A17080357 shu

Computational Insights into the Diels-Alder-alike Reactions of 1-Iodo-2-Lithio-o-Carborane with Fulvenes

Mu Weihua ^a,, ,
Ma Yao ^a ,
Fang Decai ^b ,
Wang Rong ^a ,
Zhang Haina ^a

a.
Faculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092
b.
College of Chemistry, Beijing Normal University, Beijing 100875

Corresponding author: Mu Weihua, weihua_mu@ynnu.edu.cn
Received Date: 3 August 2017
Available Online: 20 January 2017
Fund Project: the National Natural Science Foundation of China 21373030the National Natural Science Foundation of China 21763033Project supported by the National Natural Science Foundation of China (Nos. 21363028, 21763033, 21373030) and Innovative Training Program for College Students in Yunnan Provincethe National Natural Science Foundation of China 21363028

Figures(6)

Density functional theory (DFT) calculations at the B3LYP level, combining with the double-ζ valence polarized (DZVP) all-electron basis set as embeded in Gaussian 09 Program, were carried out to investigate the reaction mechanisms and substituent effect of Diels-Alder-alike reactions between 1-iodo-2-lithio-o-carborane and fulvenes. For maximum analogy with experimental conditions, all calculations were carried out in cyclohexane solution by using the IDSCRF solvent model, and all energies reported here had been adjusted adaptive to experimental temperature (353 K). According to presently obtained results, this reaction needs to go through a four-step process successively before the final carboranonorbornadiene products are formed. These four steps include forming carboryne intermediate by release of LiI fragment, interaction of carboryne with fulvenes, 1, 2-σ migration of carboranyl, and the cycloaddition process. Among all four steps mentioned above, the 1, 2-σ migration of carboranyl is predicted to be the rate-determining step (RDS), features an activation free energy barrier of 28.3 kcal·mol^-1 under experimental temperature of 353 K. A half-life of 8.7 h converted from the RDS activation free energy barrier coincides well with corresponding 56% isolated yield of carboranonorbornadiene after reacted 8 h. The LiI fragment is found to be vital in stabilizing most stationary points and driving the reaction ahead. The reaction mechanisms change little when the 4-H substituents on diphenylfulvenes (denoted reaction a) is replaced by 4-Me groups (denoted reaction b), but the corresponding RDS activation free energy barrier increased by 2.8 kcal·mol^-1 (from 28.3 to 31.1 kcal·mol^-1), transferring to a decrease in reaction rate of ca. 50 times. The obvious slower reaction rate predicted in reaction b than in reaction a gives out correct trends with an experimental yield reduction of carboranonorbornadienes from 56% to 42%, and verifies the rationality of B3LYP results in these carboranyl-involved Diels-Alder-alike reactions. Natural bond orbital (NBO) analysis about corresponding reactants and stationary points shows similar electronic characteristics of this reaction with normal-electron-demand Diels-Alder (NEDDA) reactions, i.e., the fulvenes act as electron donator when react with carboryne intermediate.
- o-carborane,
- Diels-Alder reaction,
- reaction mechanism,
- theoretical study,
- density functional theory (DFT)
1. [1]
  Li, Y.; Li, W.; Zhang, J. Chem. Eur. J. 2017, 23, 467. doi: 10.1002/chem.201602822
2. [2]
  Pellissier, H. Chem. Rev. 2016, 116, 14868. doi: 10.1021/acs.chemrev.6b00639
3. [3]
  Wei, L.; Wang, C.-J. Chem. Commun. 2015, 51, 15374. doi: 10.1039/C5CC06465A
4. [4]
  Ai, W.; Liao, D.; Lei, X. Chin. J. Org. Chem. 2015, 35, 1615(in Chinese).
5. [5]
  Liu, W.; Wu, Y.; Li, L.; Li, X. Chin. J. Org. Chem. 2016, 36, 1501(in Chinese).
6. [6]
  Cao, M.-H.; Green, N. J.; Xu, S.-Z. Org. Biomol. Chem. 2017, 15, 3105. doi: 10.1039/C6OB02761J
7. [7]
  Xie, M.; Lin, L.; Feng, X. Chem. Rec. 2017, 17, 1.
8. [8]
  Fang, D.; Chen, Y. Acta Chim. Sinica 2014, 72, 253(in Chinese).
9. [9]
  Ran, Y.; Tang, M.; Wang, Y.; Wang, Y.; Zhang, X.; Zhu, Y.; Wei, D.; Zhang, W. Tetrahedron 2016, 72, 5295. doi: 10.1016/j.tet.2016.06.057
10. [10]
  Musavi, S. M.; Amani, J.; Omidian, N. Tetrahedron 2014, 70, 708. doi: 10.1016/j.tet.2013.11.089
11. [11]
  Li, Y.; Fang, D.-C. Phys. Chem. Chem. Phys. 2014, 16, 15224. doi: 10.1039/c4cp02068e
12. [12]
  Tang, M.; Wu, Y.; Liu, Y.; Cai, M.; Xia, F.; Liu, S.; Hu, W. Acta Chim. Sinica 2016, 74, 54(in Chinese). doi: 10.7503/cjcu20150436
13. [13]
  Yang, Y.-F.; Liang, Y.; Liu, F.; Houk, K. N. J. Am. Chem. Soc. 2016, 138, 1660. doi: 10.1021/jacs.5b12054
14. [14]
  Duan, A.; Yu, P.; Liu, F.; Qiu, H.; Gu, F. L.; Doyle, M. P.; Houk, K. N. J. Am. Chem. Soc. 2017, 139, 2766. doi: 10.1021/jacs.6b12371
15. [15]
  Yang, Y.; Liu, Q.; Zhang, L.; Yu, H.; Dang, Z. Organometallics 2017, 36, 687. doi: 10.1021/acs.organomet.6b00886
16. [16]
  Li, Y.; Du, S. RSC Adv. 2016, 6, 84177. doi: 10.1039/C6RA16321A
17. [17]
  Diamond, O. J.; Marder, T. B. Org. Chem. Front. 2017, 4, 891. doi: 10.1039/C7QO00071E
18. [18]
  Ess, D. H.; Jones, G. O.; Houk, K. N. Adv. Synth. Catal. 2006, 348, 2337. doi: 10.1002/(ISSN)1615-4169
19. [19]
  Yu, P.; Yang, Z.; Liang, Y.; Hong, X.; Li, Y.; Houk, K. N. J. Am. Chem. Soc. 2016, 138, 8247. doi: 10.1021/jacs.6b04113
20. [20]
  Yu, P.; Li, W.; Houk, K. N. J. Org. Chem. 2017, 82, 6398. doi: 10.1021/acs.joc.7b01132
21. [21]
  Pellissier, H. Adv. Synth. Catal. 2016, 358, 2194. doi: 10.1002/adsc.v358.14
22. [22]
  Mojica, M.; Méndez, F.; Alonso, J. A. Molecules 2016, 21, 200. doi: 10.3390/molecules21020200
23. [23]
  Oliveira, B. L.; Guo, Z.; Bernardes, G. J. L. Chem. Soc. Rev. 2017, 46, 4895. doi: 10.1039/C7CS00184C
24. [24]
  Fell, J. S.; Lopez, S. A.; Higginson, C. J.; Finn, M. G.; Houk, K. N. Org. Lett. 2017, 19, 4504. doi: 10.1021/acs.orglett.7b02064
25. [25]
  Liu, F.; Liang, Y.; Houk, K. N. J. Am. Chem. Soc. 2014, 136, 11483. doi: 10.1021/ja505569a
26. [26]
  Levandowski, B. J.; Zou, L.; Houk, K. N. J. Comput. Chem. 2016, 37, 117. doi: 10.1002/jcc.24191
27. [27]
  Zhang, J.; Qiu, Z.; Xu, P.-F.; Xie, Z. ChemPlusChem 2014, 79, 1044. doi: 10.1002/cplu.201402129
28. [28]
  Tang, C.; Xie, Z. Angew. Chem., Int. Ed. 2015, 54, 7662. doi: 10.1002/anie.201502502
29. [29]
  (a) Lyu, H.; Quan, Y.; Xie, Z. Angew. Chem., Int. Ed. 2015, 54, 10623; (b) Lyu, H.; Quan, Y.; Xie, Z. J. Am. Chem. Soc. 2016, 138, 12727.
30. [30]
  Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
31. [31]
  Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
32. [32]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; 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.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford, CT, 2013.
33. [33]
  Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899. doi: 10.1021/cr00088a005
34. [34]
  Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735. doi: 10.1063/1.449486
35. [35]
  Carpenter, J. E.; Weinhold, F. J. Mol. Struct. 1988, 169, 41. doi: 10.1016/0166-1280(88)80248-3
36. [36]
  Zhao, D.; Zhang, J.; Xie, Z. Angew. Chem., Int. Ed. 2014, 53, 12902. doi: 10.1002/anie.201409141
37. [37]
  Qiu, Z.; Xie, Z. Dalton Trans. 2014, 43, 4925. doi: 10.1039/C3DT52711E
38. [38]
  Wang, S. R.; Xie, Z. Organometallics 2012, 31, 4544. doi: 10.1021/om300324n
39. [39]
  Qiu, Z.; Ren, S.; Xie, Z. Acc. Chem. Res. 2011, 44, 299. doi: 10.1021/ar100156f
40. [40]
  Dang, Y.; Qu, S.; Tao, Y.; Song, C.; Wang, Z. X. J. Org. Chem. 2014, 79, 9046. doi: 10.1021/jo501399x
41. [41]
  Dub, P. A.; Béthegnies, A.; Poli, R. Organometallics 2012, 31, 294. doi: 10.1021/om2009149
42. [42]
  Godbout, N.; Salahub, D. R.; Andzelm, J.; Wimmer, E. Can. J. Chem. 1992, 70, 560. doi: 10.1139/v92-079
43. [43]
  Sosa, C.; Andzelm, J.; Elkin, B. C.; Wimmer, E.; Dobbs, K. D.; Dixon, D. A. J. Phys. Chem. 1992, 96, 6630. doi: 10.1021/j100195a022
44. [44]
  Miertus, S.; Scrocco, E.; Tomasi, J. Chem. Phys. 1981, 55, 117. doi: 10.1016/0301-0104(81)85090-2
45. [45]
  Tao, J.-Y.; Mu, W.-H.; Chass, G. A.; Tang, T.-H.; Fang, D.-C. Int. J. Quantum Chem. 2013, 113, 975. doi: 10.1002/qua.24065
46. [46]
  Fang, D.-C. THERMO, Beijing Normal University, Beijing, China.
47. [47]
  Gonzalez, C.; Schlegel, H. B. J. Chem. Phys. 1989, 90, 2154. doi: 10.1063/1.456010
48. [48]
  Gonzalez, C.; Schlegel, H. B. J. Phys. Chem. 1990, 94, 5523. doi: 10.1021/j100377a021
49. [49]
  Fukui, K. Acc. Chem. Res. 1981, 14, 363. doi: 10.1021/ar00072a001
50. [50]
  Grimme, S. J. Comput. Chem. 2006, 27, 1787. doi: 10.1002/(ISSN)1096-987X
51. [51]
  Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys. 2010, 132, 154104. doi: 10.1063/1.3382344
52. [52]
  Chai, J.-D.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2008, 10, 6615. doi: 10.1039/b810189b
53. [53]
  Zhao, Y.; Truhlar, D. G. J. Phys. Chem. 2006, 110, 5121. doi: 10.1021/jp060231d
54. [54]
  Mu, W. H.; Xia, S. Y.; Li, J. X.; Fang, D. C.; Wei, G.; Chass, G. A. J. Org. Chem. 2015, 80, 9108. doi: 10.1021/acs.joc.5b01464
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