A one-pot synthesis of a self-included bisester-functionalized copillar[5]arene

Qiong Jia Xusheng Du Chunyu Wang Kamel Meguellati

Citation:  Jia Qiong, Du Xusheng, Wang Chunyu, Meguellati Kamel. A one-pot synthesis of a self-included bisester-functionalized copillar[5]arene[J]. Chinese Chemical Letters, 2019, 30(3): 721-724. doi: 10.1016/j.cclet.2018.12.015 shu

A one-pot synthesis of a self-included bisester-functionalized copillar[5]arene

English

  • Pillar[n]arenes [1-5] have been a promising class of macrocycles constituted by 1, 4-dimethoxylbenzene rings linked by methylene bridges with a symmetric, rigid and tunable structure [6-12]. Several practical applications, such as host-guest chemistry [13-18], sensors [19-29], molecular machines [30-33], selfassemblies [34-36], drug delivery [37-40] and hybrid organicinorganic materials [41, 42] have been reported. These applications were mostly based on the functionalization of pillar[n]arenes by functionalizing the rims and controlling their solubility in water and organic solvents. The commonly used methodologies for the functionalization of pillar[5]arene involves one or multiple monomers that cyclize in the presence of a Brønsted acid or Lewis acid catalyst, and post synthetic modifications can lead to mono-, bis- and multi-substituted pillar[5]arene.

    The first fully substituted pillar[5]arene was reported by Ogoshi [43], and the portfolio of their functionalization was extended to the conception of artificial transmembrane proton channel [44], stabilization of gold nanoparticles [45], construction of particular molecular machines and so on. Mono-substituted elegant methodology of synthetic post-modification involving the oxidation of a ring followed by a regioselective reduction pillar[5]arene was reported by Cao's group by adopting an ester group into a phenolic motif which was subsequently substituted [46]. The methodology to the direct construction of monoester-substituted pillar[5]arene has also been poorly exploited by direct cyclization with 2 monomers [47, 48]. These unique monoester-substituted pillar[5] arene can be used not only for molecular recognition but also for the construction of stable [1]rotaxanes with potential catalytic capacities, and multi-pillar[5]arene metallacycles [49].

    Due to their wide applications, easier methods to produce bisester-functionalized copillar[5]arene are still on demand. Based on our previous work [47], we found that the precursor, diethyl 2, 2'-(1, 4-phenylenebis(oxy))diacetate (M), was appropriate for the construction of bisester-functionalized copillar[5]arene (BECP5A), which is more efficient and economic than the reported synthetic methodology that at least required four steps (with an overall yield of 28%), as shown in Scheme 1. In this work, BECP5A was deeply investigated both in solution and in solid state with the aid of 2D NMR spectrum and X-ray crystal diffraction.

    Scheme 1

    Scheme 1.  Synthetic methodologies of BECP5A by post-modification and premodification: Route Ⅰ (blue) and Route Ⅱ (red).

    Following another synthetic route (Route Ⅱ), hydroquinone was reacted with ethyl bromoacetate leading to the ester containing precursor M, then the condition to synthesize BECP5A was optimized, among which the most suitable one was described as: 1, 4-dimethoxybenzene (30.0 mmol) in dichloromethane (250.0 mL) was added paraformaldehyde (109.5 mmol) and M (6.0 mmol), then the suspension was stirred at 0 ℃ for 30 min, then boron trifluoride diethyl etherate (42.5 mmol) was added, and the mixture was stirred at 0 ℃ for 90 min. The final compound was obtained with yield up to 20%.

    The obtained compound was firstly analyzed by electrospray ionization mass spectra (Figs. S9 and S10 in Supporting information) which gave m/z calcd. for C51H59O14+ [M+H]+: 895.390; found: 895.391. Calcd. for C51H62NO14+ [M + NH4]+: 912.416; found: 912.415. Calcd. for C51H58NaO14+ [M + Na]+: 917.372; found: 917.370. Calcd. for C51H58KO14+ [M + K]+: 933.346; found: 933.342. Compound BECP5A was characterized by 1H NMR and 13C NMR spectra (Figs. S5-S8 in Supporting information). When CDCl3 was used as the solvent, a strong sharp triplex peak appeared in the range of high-field chemical value below 0 ppm, which indicated that BECP5A is potentially self-included in chloroform. To further investigate this phenomenon, the comparison of the NMR spectra of M and BECP5A was done and shown in Fig. 1. From Fig. 1a, HA' and HB' were up-field shifted to δ 3.13 and δ -0.26, compared to δ 4.26 and δ 1.29, respectively from M. The ΔδH of HA and HB were found to be 1.13 ppm and 1.55 ppm, respectively. From Fig. 1b, 13C chemical shifts of CA' and CB' were upfield shifted to δ 61.2 and δ 12.6, compared to δ 61.5 and δ 14.4, respectively. The ΔδC of CA and CB were found to be 0.3 ppm and 1.8 ppm. These obvious chemical shift changes were further supported by Nuclear Overhauser Effect Spectroscopy (NOESY) where the proximity between the protons has to be below 5 Å to see the spatial correlations. From Fig. 2, it is clear that HA' and HB' are all close to the methylene bridges or methoxy groups HC, D and benzylic hydrogens, HAr. However, the difference of chemical shifts Δδ value were found to be low when DMSO-d6 was used as the solvent. To further give a convinced evidence, one equivalent of malononitrile was added to a solution of BECP5A in CDCl3, and an obvious downfield shift of the ethyl groups to 3.55 ppm for HA' and 0.29 ppm for HB' were observed by displacement (Fig. S14 in Supporting information). We can conclude that in solution, BECP5A have a symmetric and self-included conformation in chloroform where the cavity hosts the pair of ester groups which is not the case in DMSO.

    Figure 1

    Figure 1.  1H NMR (a) and partial 13C NMR spectra (b) of M and BECP5A in CDCl3.

    Figure 2

    Figure 2.  Partial NOESY spectrum (600 MHz, CDCl3, 298 K) of BECP5A.

    Based on the above conclusions, we were wondering if the cavity of pillar[5]arene can host a pair of ester groups in the solid state. For this purpose, the single crystal was grown by slow evaporation of a solution in chloroform/methanol. Although the difficulties of obtain the crystal structure, we finally solved the crystal structure as shown in Figs. 3a-c. The real structure of BECP5A exists with only one side of ester group hosted in the cavity of pillar[5]arene excluding the other one outer the cavity. From Figs. 3a and b, the intramolecular C-H…π interactions and C- H…O interactions play a vital role in the stabilization of this selfincluded conformation (Fig. S16 in Supporting information). We found from the crystal structure two prochiral conformations (pS and pR) contained in a unit cell which are shown in Fig. 3c.

    Figure 3

    Figure 3.  X-ray crystal structure of a selected pS conformation of BECP5A: a) side view, b) top view, c) pR and pS conformations, d) C-H…O interaction between chloroform and carboxylate oxygen of BECP5A, e) dihedral angle between bisester-functionalized benzene ring and the plane of copillar[5]arene, f) intermolecular C-H…π and g) ππ interactions of BECP5A. Packing mode of BECP5A along h) [100], i) [010], j) [001] directions. Parts of hydrogen atoms have been omitted for clarity. C: grey, O: red. Cl: green.

    Additional investigations of the crystal structure are shown in Figs. 3d-g. From Fig. 3d, we noticed strong C-H…O interactions between the hydrogens belonging to chloroform and oxygen of one carboxylate group, which contributes to the stabilization of the asymmetrical structure of BECP5A. Figs. 3f-g show that there exists intermolecular C-H…π and ππ interactions of BECP5A. The dihedral angle between bisester-functionalized benzene ring and the plane of copillar[5]arene in BECP5A was measured to 67.22°, as shown in Fig. 3e.

    The ratio of CDCl3/CD3OD was fluctuated to see the effects on the self-inclusion (Fig. S14 in Supporting information), an increased ratio of methanol led to the removal of the ester groups from the cavity proving that the polarity of methanol breaks the stabilizing interactions in favor of the self-inclusion.

    In conclusion, a bisester-substituted pillar[5]arene was synthesized by a one-pot reaction with yield up to 20% and fully characterized by 1H NMR, 13C NMR, NOESY, LC-MS and X-ray crystal structure. The properties of a such molecule were deeply investigated in the solution state, showing that this molecule displayed a symmetric and self-included conformation with the two ester groups hosted in the cavity but in a partial self-included conformation in DMSO than chloroform due to the difference of polarity of solvents, and in the solid state, demonstrating that the compound has an asymmetrical structure with only one ester in the cavity of pillar[5]arene. Further applications of BECP5A has been explored in our lab and is an interesting intermediate for the construction of mechanically interlocked structure or polymers.

    We thank the JLU Cultivation Fund for the National Science Fund for Distinguished Young Scholars, and NMAC, College of Chemistry at Jilin University for financial support.

    Supplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.cclet.2018.12.015.

    1. [1]

      T. Ogoshi, S. Kanai, S. Fujinami, T.-a. Yamagishi, Y. Nakamoto, J. Am. Chem. Soc. 130(2008) 5022-5023. doi: 10.1021/ja711260m

    2. [2]

      P.J. Cragg, K. Sharma, Chem. Soc. Rev. 41(2012) 597-607. doi: 10.1039/C1CS15164A

    3. [3]

      T. Ogoshi, T.-a. Yamagishi, Y. Nakamoto, Chem. Rev. 116(2016) 7937-8002. doi: 10.1021/acs.chemrev.5b00765

    4. [4]

      M. Xue, Y. Yang, X. Chi, Z. Zhang, F. Huang, Acc. Chem. Res. 45(2012) 1294-1308. doi: 10.1021/ar2003418

    5. [5]

      T. Kakuta, T.-a. Yamagishi, T. Ogoshi, Acc. Chem. Res. 51(2018) 1656-1666. doi: 10.1021/acs.accounts.8b00157

    6. [6]

      X.B. Hu, Z. Chen, G. Tang, J.L. Hou, Z.T. Li, J. Am. Chem. Soc. 134(2012) 8384-8387. doi: 10.1021/ja302292c

    7. [7]

      D.R. Cao, Y.H. Kou, J.Q. Liang, et al., Angew. Chem. 121(2009) 9901-9903. doi: 10.1002/ange.200904765

    8. [8]

      J.F. Stoddart, N.L. Strutt, R.S. Forgan, J.M. Spruell, Y.Y. Botros, J. Am. Chem. Soc. 133(2011) 5668-5671. doi: 10.1021/ja111418j

    9. [9]

      Z.B. Zhang, B.Y. Xia, C.Y. Han, Y.H. Yu, F.H. Huang, Org. Lett. 12(2010) 3285-3287. doi: 10.1021/ol100883k

    10. [10]

      C.J. Li, K. Han, J. Li, et al., Org. Lett. 14(2012) 42-45. doi: 10.1021/ol2027834

    11. [11]

      J.R. Wu, C.Y. Wang, Y.C. Tao, et al., Eur. J. Org. Chem. 2018(2018) 1321-1325. doi: 10.1002/ejoc.v2018.11

    12. [12]

      J.R. Wu, A.U. Mu, B. Li, et al., Angew. Chem. Int. Ed. 57(2018) 9853-9858. doi: 10.1002/anie.201805980

    13. [13]

      X.B. Hu, L. Chen, W. Si, Y. Yu, J.L. Hou, Chem. Commun. 47(2011) 4694-4696. doi: 10.1039/c1cc10633c

    14. [14]

      Y.J. Ma, X.F. Ji, F. Xiang, et al., Chem. Commun. 47(2011) 12340-12342. doi: 10.1039/c1cc15660h

    15. [15]

      T. Ogoshi, J. Incl. Phenom. Macrocycl. Chem. 72(2012) 247-262. doi: 10.1007/s10847-011-0027-2

    16. [16]

      F.H. Huang, Z.B. Zhang, Y. Luo, et al., Angew. Chem. 123(2011) 1433-1437. doi: 10.1002/ange.v123.6

    17. [17]

      Z.B. Zhang, G.C. Yu, C.Y. Han, et al., Org. Lett. 13(2011) 4818-4821. doi: 10.1021/ol2018938

    18. [18]

      X.Y. Shu, S.H. Chen, J. Li, et al., Chem. Commun. 48(2012) 2967-2969. doi: 10.1039/c2cc00153e

    19. [19]

      J.H. Bi, X.F. Zeng, D.M. Tian, H.B. Li, Org. Lett. 18(2016) 1092-1095. doi: 10.1021/acs.orglett.6b00097

    20. [20]

      Y.C. Chang, K. Yang, P. Wei, et al., Angew. Chem. 53(2014) 13126-13130. doi: 10.1002/anie.201407272

    21. [21]

      P. Wang, Y. Yao, M. Xue, Chem. Commun. 50(2014) 5064-5067. doi: 10.1039/C4CC01403K

    22. [22]

      X. Wu, Y. Li, C. Lin, X.Y. Hu, L.Y. Wang, Chem. Commun. 51(2015) 6832-6835. doi: 10.1039/C5CC01393C

    23. [23]

      Q.F. Yao, B.Z. Lv, C.D. Ji, Y. Cai, M.Z. Yin, ACS Appl. Mater. Interfaces 9(2017) 36320-36326. doi: 10.1021/acsami.7b12063

    24. [24]

      G.C. Yu, C.Y. Han, Z.B. Zhang, et al., J. Am. Chem. Soc. 134(2012) 8711-8717. doi: 10.1021/ja302998q

    25. [25]

      F. Zhang, J.K. Ma, Y. Sun, et al., Chem. Sci. 7(2016) 3227-3233. doi: 10.1039/C5SC04726A

    26. [26]

      H.T.Z. Zhu, L.Q. Shangguan, B.B. Shi, G.C. Yu, F.H. Huang, Mater. Chem. Front. 2(2018) 2152-2174. doi: 10.1039/C8QM00314A

    27. [27]

      J.F. Chen, Q. Lin, Y.M. Zhang, H. Yao, T.B. Wei, Chem. Commun. 53(2017) 13296-13311. doi: 10.1039/C7CC08365C

    28. [28]

      X. Li, Z. Li, Y.W. Yang, Adv. Mater. 30(2018) 1800177. doi: 10.1002/adma.v30.20

    29. [29]

      X.Y. Jin, N. Song, X. Wang, et al., Sci. Rep. 8(2018) 4035. doi: 10.1038/s41598-018-22446-y

    30. [30]

      T. Ogoshi, D. Yamafuji, T.-a. Yamagishi, A.M. Brouwer, Chem. Commun. 49(2013) 5468-5470. doi: 10.1039/c3cc42612b

    31. [31]

      X. Wu, M.F. Ni, W. Xia, X.Y. Hu, L.Y. Wang, Org. Chem. Front. 2(2015) 1013-1017. doi: 10.1039/C5QO00159E

    32. [32]

      X.Z. Yan, P.F. Wei, Z.T. Li, et al., Chem. Commun. 49(2013) 2512-2514. doi: 10.1039/c3cc40474a

    33. [33]

      X.Z. Yan, B. Zheng, F.H. Huang, Polym. Chem. 4(2013) 2395-2399. doi: 10.1039/c3py00060e

    34. [34]

      C.J. Li, X.Y. Shu, J. Li, et al., Org. Lett. 14(2012) 4126-4129. doi: 10.1021/ol301757q

    35. [35]

      X. Wu, Y. Yu, L. Gao, X.Y. Hu, L.Y. Wang, Org. Chem. Front. 3(2016) 966-970. doi: 10.1039/C6QO00197A

    36. [36]

      H.C. Zhang, Y.L. Zhao, Chem. Eur. J. 19(2013) 16862-16879. doi: 10.1002/chem.v19.50

    37. [37]

      L.Y. Gao, B. Zheng, W. Chen, C.A. Schalley, Chem. Commun. 51(2015) 14901-14904. doi: 10.1039/C5CC06207A

    38. [38]

      K. Yang, Y.C. Chang, J. Wen, et al., Chem. Mater. 28(2016) 1990-1993. doi: 10.1021/acs.chemmater.6b00696

    39. [39]

      Y.J. Zhou, K.C. Jie, F.H. Huang, Chem. Commun. 53(2017) 8364-8367. doi: 10.1039/C7CC04779G

    40. [40]

      X.Y. Shu, K.D. Xu, D.B. Hou, C.J. Li, Isr. J. Chem. 58(2018) 1194-1204. doi: 10.1002/ijch.201800013

    41. [41]

      J.F. Chen, X. Liu, J.F. Ma, et al., Soft Matter 13(2017) 5214-5218. doi: 10.1039/C7SM01118K

    42. [42]

      N. Song, T. Kakuta, T.-a. Yamagishi, Y.W. Yang, T. Ogoshi, Chem 4(2018) 2029-2053. doi: 10.1016/j.chempr.2018.05.015

    43. [43]

      T. Ogoshi, M. Hashizume, T.-a. Yamagishi, Y. Nakamoto, Chem. Commun. 46(2010) 3708-3710. doi: 10.1039/c0cc00348d

    44. [44]

      W. Si, L. Chen, X.B. Hu, et al., Angew. Chem. 123(2011) 12772-12776. doi: 10.1002/ange.201106857

    45. [45]

      H. Li, D.X. Chen, Y.L. Sun, et al., J. Am. Chem. Soc. 135(2013) 1570-1576. doi: 10.1021/ja3115168

    46. [46]

      Y. Chen, D. Cao, L. Wang, et al., Chem. Eur. J. 19(2013) 7064-7070. doi: 10.1002/chem.v19.22

    47. [47]

      X.S. Du, C.Y. Wang, Q. Jia, et al., Chem. Commun. 53(2017) 5326-5329. doi: 10.1039/C7CC02364B

    48. [48]

      Y. Han, G.F. Huo, J. Sun, et al., Sci. Rep. 6(2016) 28748. doi: 10.1038/srep28748

    49. [49]

      Z.Y. Li, Y. Zhang, C.W. Zhang, et al., J. Am. Chem. Soc. 136(2014) 8577-8589. doi: 10.1021/ja413047r

  • Scheme 1  Synthetic methodologies of BECP5A by post-modification and premodification: Route Ⅰ (blue) and Route Ⅱ (red).

    Figure 1  1H NMR (a) and partial 13C NMR spectra (b) of M and BECP5A in CDCl3.

    Figure 2  Partial NOESY spectrum (600 MHz, CDCl3, 298 K) of BECP5A.

    Figure 3  X-ray crystal structure of a selected pS conformation of BECP5A: a) side view, b) top view, c) pR and pS conformations, d) C-H…O interaction between chloroform and carboxylate oxygen of BECP5A, e) dihedral angle between bisester-functionalized benzene ring and the plane of copillar[5]arene, f) intermolecular C-H…π and g) ππ interactions of BECP5A. Packing mode of BECP5A along h) [100], i) [010], j) [001] directions. Parts of hydrogen atoms have been omitted for clarity. C: grey, O: red. Cl: green.

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  • 发布日期:  2019-03-22
  • 收稿日期:  2018-10-19
  • 接受日期:  2018-12-12
  • 修回日期:  2018-12-04
  • 网络出版日期:  2018-03-13
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