Reaction of Bromoacetyl and Sulfhydryl Groups: Efficient Synthesis of Aromatic Oligoamides Consisting of Benzene-1,3,5-tricarboxamide Units

Bao Luan; Qingfei Huang; Lei Wang; Jingen Deng; Menglan Lv; Qiwei Wang; Jin Zhu

doi:10.1055/s-0035-1560510

Synlett, Table of Contents

Synlett 2016; 27(02): 225-230
DOI: 10.1055/s-0035-1560510

letter

Reaction of Bromoacetyl and Sulfhydryl Groups: Efficient Synthesis of Aromatic Oligoamides Consisting of Benzene-1,3,5-tricarboxamide Units

Authors

Bao Luan

^aChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China Email: jinzhu@cioc.ac.cn

^bGraduate University of Chinese Academy of Sciences, Beijing 100049, P. R. of China
Qingfei Huang

^aChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China Email: jinzhu@cioc.ac.cn
Lei Wang

^aChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China Email: jinzhu@cioc.ac.cn
Jingen Deng

^cWest China School of Pharmacy, Sichuan University, Chengdu 610041, P. R. of China
Menglan Lv

^aChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China Email: jinzhu@cioc.ac.cn
Qiwei Wang*

^aChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China Email: jinzhu@cioc.ac.cn
Jin Zhu*

^aChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. of China Email: jinzhu@cioc.ac.cn

Abstract

All articles of this category

Abstract

A series of aromatic oligoamides consisting of benzene-1,3,5-tricarboxamide (BTA) residues linked by thioether bonds were designed and synthesized based on the highly efficient and specific reaction between sulfhydryl and bromoacetyl groups. Initial assessment of the folding of these oligoamides with circular dichroism (CD) spectroscopy showed that these oligoamides could fold into a helical conformation.

Key words

benzene-1,3,5-tricarboxamides - bromoacetyl group - sulfhydryl group - oligoamides - circular dichroism - folded conformation

Full Text

References

References and Notes

1a Brunsveld L, Schenning AP, Broeren MA, Janssen HM, Vekemans JA, Meijer EW. Chem. Lett. 2000; 292
1b Kristiansen PM, Gress A, Smith P, Hanft D, Schmidt H.-W. Polymer 2006; 47: 249
1c Roosma J, Mes T, Leclère P, Palmans AR, Meijer EW. J. Am. Chem. Soc. 2008; 130: 1120
1d Smulders MM, Filot IA, Leenders JM, van der Schoot P, Palmans AR, Schenning AP, Meijer EW. J. Am. Chem. Soc. 2009; 132: 611
1e Stals PJ, Haveman JF, Palmans AR, Schenning AP. J. Chem. Educ. 2009; 86: 230
1f Yang Y, Xue M, Xiang J, Chen C. J. Am. Chem. Soc. 2009; 131: 12657
1g Stals PJ, Smulders MM, Martín-Rapún R, Palmans AR, Meijer EW. Chem. Eur. J. 2009; 15: 2071
1h Filot IA, Palmans AR, Hilbers PA, van Santen RA, Pidko EA, de Greef TF. J. Phys. Chem. B 2010; 114: 13667
1i Stals PJ, Everts JC, de Bruijn R, Filot IA, Smulders MM, Martin-Rapun R, Pidko EA, de Greef TF, Palmans AR, Meijer EW. Chemistry 2010; 16: 810
1j Cantekin S, Balkenende DW, Smulders MM, Palmans AR, Meijer EW. Nat. Chem. 2011; 3: 42
1k Terashima T, Mes T, De Greef TF, Gillissen MA, Besenius P, Palmans AR, Meijer EW. J. Am. Chem. Soc. 2011; 133: 4742
1l Cantekin S, Nakano Y, Everts JC, van der Schoot P, Meijer EW, Palmans AR. Chem. Commun. 2012; 48: 3803
1m Veling N, van Hameren R, van Buul AM, Rowan AE, Nolte RJ, Elemans JA. Chem. Commun. 2012; 48: 4371
1n Garcia F, Korevaar PA, Verlee A, Meijer EW, Palmans AR, Sanchez L. Chem. Commun. 2013; 49: 8674
1o Yang Y, Huang F, Chen C, Xia M, Cai Q, Qian F, Xiang J. Sci. Rep. 2013; 3: 1059
1p Gillissen MA. J, Terashima T, Meijer EW, Palmans AR. A, Voets IK. Macromolecules 2013; 46: 4120
1q Narayan B, Kulkarni C, George SJ. J. Mater. Chem. C 2013; 1: 626
1r Gillissen MA, Koenigs MM, Spiering JJ, Vekemans JA, Palmans AR, Voets IK, Meijer EW. J. Am. Chem. Soc. 2014; 136: 336

2a Ryu SY, Kim S, Seo J, Kim Y.-W, Kwon O.-H, Jang D.-J, Park SY. Chem. Commun. 2004; 70
2b Danila I, Riobé F, Puigmartí-Luis J, Del Pino ÁP, Wallis JD, Amabilino DB, Avarvari N. J. Mater. Chem. 2009; 19: 4495
2c Veld MA. J, Haveman D, Palmans AR. A, Meijer EW. Soft Matter 2011; 7: 524
2d Cantekin S, de Greef TF, Palmans AR. Chem. Soc. Rev. 2012; 41: 6125
2e Aparicio F, García F, Sánchez L. Chem. Eur. J. 2013; 19: 3239
2f Howe RC, Smalley AP, Guttenplan AP, Doggett MW, Eddleston MD, Tan JC, Lloyd GO. Chem. Commun. 2013; 49: 4268
2g Leung M.-k, Lin Y.-S, Lee C.-C, Chang C.-C, Wang Y.-X, Kuo C.-P, Singh N, Lin K.-R, Hu C.-W, Tseng C.-Y, Ho K.-C. RSC Adv. 2013; 3: 22219
2h Raynal M, Portier F, van Leeuwen PW, Bouteiller L. J. Am. Chem. Soc. 2013; 135: 17687
2i Bejagam KK, Fiorin G, Klein ML, Balasubramanian S. J. Phys. Chem. B 2014; 118: 5218
2j Hosono N, Pitet LM, Palmans AR. A, Meijer EW. Polym. Chem. 2014; 5: 1463
2k Hosono N, Stals PJ, Palmans AR, Meijer EW. Chem Asian J. 2014; 9: 1099
2l Leenders CM, Mes T, Baker MB, Koenigs MM, Besenius P, Palmans AR, Meijer EW. Mater. Horiz. 2014; 1: 116
2m Stals PJ, Gillissen MA, Paffen TF, de Greef TF, Lindner P, Meijer EW, Palmans AR, Voets IK. Macromolecules 2014; 47: 2947

3a Lightfoot MP, Mair FS, Pritchard RG, Warren JE. Chem. Commun. 1999; 1945
3b Wilson AJ, Masuda M, Sijbesma RP, Meijer EW. Angew. Chem. Int. Ed. 2005; 44: 2275
3c Sakamoto A, Ogata D, Shikata T, Urakawa O, Hanabusa K. Polymer 2006; 47: 956
3d Wilson AJ, van Gestel J, Sijbesma RP, Meijer EW. Chem. Commun. 2006; 4404
3e Fitié CF, Tomatsu I, Byelov D, de Jeu WH, Sijbesma RP. Chem. Mater. 2008; 20: 2394
3f Smulders MM, Schenning AP, Meijer EW. J. Am. Chem. Soc. 2008; 130: 606
3g Demenev A, Eichhorn SH, Taerum T, Perepichka DF, Patwardhan S, Grozema FC, Siebbeles LD, Klenkler R. Chem. Mater. 2010; 22: 1420

4 Klosterman JK, Yamauchi Y, Fujita M. Chem. Soc. Rev. 2009; 38: 1714

5a Breidenbach S, Ohren S, Nieger M, Vogtle F. J. Chem. Soc., Chem. Commun. 1995; 1237
5b Lokey RS, Iverson BL. Nature (London, U.K.) 1995; 375: 303
5c Gabriel GJ, Sorey S, Iverson BL. J. Am. Chem. Soc. 2005; 127: 2637
5d Cao J, Kline M, Chen Z, Luan B, Lv M, Zhang W, Lian C, Wang Q, Huang Q, Wei X, Deng J, Zhu J, Gong B. Chem. Commun. 2012; 48: 11112

6 Zhang W, Horoszewski D, Decatur J, Nuckolls C. J. Am. Chem. Soc. 2003; 125: 4870
7 Chen Z, Urban ND, Gao Y, Zhang W, Deng J, Zhu J, Zeng XC, Gong B. Org. Lett. 2011; 13: 4008

8a Jones PB, Parrish NM, Houston TA, Stapon A, Bansal NP, Dick JD, Townsend CA. J. Med. Chem. 2000; 43: 3304
8b Loghmani-Khouzani H, Poorheravi MR, Sadeghi MM, Caggiano L, Jackson RF. Tetrahedron 2008; 64: 7419
8c Gagnon A, Landry S, Coulombe R, Jakalian A, Guse I, Thavonekham B, Bonneau PR, Yoakim C, Simoneau B. Bioorg. Med. Chem. Lett. 2009; 19: 1199
8d Su X, Pradaux-Caggiano F, Thomas MP, Szeto MW, Halem HA, Culler MD, Vicker N, Potter BV. ChemMedChem 2010; 5: 1026
8e Akremi A, Beji M, Baklouti A. Synth. Commun. 2011; 41: 1990
8f Airoldi C, Mourtas S, Cardona F, Zona C, Sironi E, D’Orazio G, Markoutsa E, Nicotra F, Antimisiaris SG, La Ferla B. Eur. J. Med. Chem. 2014; 85: 43

9a Lin P.-C, Ueng S.-H, Tseng M.-C, Ko J.-L, Huang K.-T, Yu S.-C, Adak AK, Chen Y.-J, Lin C.-C. Angew. Chem. Int. Ed. 2006; 45: 4286
9b Paulick MG, Wise AR, Forstner MB, Groves JT, Bertozzi CR. J. Am. Chem. Soc. 2007; 129: 11543
9c Peterle T, Leifert A, Timper J, Sologubenko A, Simon U, Mayor M. Chem. Commun. 2008; 3438
9d Lu J.-Y, Riedrich M, Mikyna M, Arndt H.-D. Angew. Chem. Int. Ed. 2009; 48: 8137
9e Fenton JM, Busse M, Rendina LM. Aust. J. Chem. 2015; 68: 576

10a Dolain C, Jiang H, Léger J.-M, Guionneau P, Huc I. J. Am. Chem. Soc. 2005; 127: 12943
10b Hu H.-Y, Xiang J.-F, Yang Y, Chen C.-F. Org. Lett. 2008; 10: 1275

11 Selected Spectroscopic Data Compound 2-1 ¹H NMR (300 MHz, CDCl₃): δ = 0.87–0.94 (m, 6 H), 1.30–1.41 (m, 8 H), 1.57–1.66 (m, 4 H), 4.08–4.22 (m, 2 H), 4.82–4.87 (m, 1 H), 7.37 (d, J = 6.99 Hz, 1 H), 8.96 (m, 2 H), 9.16 (m, 1 H) ppm. Compound 2: ¹H NMR (300 MHz, CDCl₃): δ = 0.90–0.92 (m, 11 H), 1.25–1.40 (m, 16 H), 1.53 (d, J = 7.5 Hz, 3 H), 1.65–1.72 (m, 6 H), 2.35 (t, J = 7.5 Hz, 4 H), 3.99–4.17 (m, 2 H), 4.67–4.75 (m, 1 H), 7.11 (d, J = 7.2 Hz, 1 H), 7.69 (s, 2 H), 7.78 (s, 2 H), 8.00 (s, 1 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 13.9, 14.0,18.0, 22.4, 22.9, 23.7, 23.8, 25.2, 28.9, 30.3, 30.4, 31.4, 37.5, 38.8, 38.8, 49.0, 68.0, 113.8, 114.0, 135.0, 139.0, 167.0, 172.2, 173.3 ppm. ESI-HRMS: m/z calcd for C₃₀H₄₉N₃O₅Na [M + Na]⁺: 554.3570; found: 554.3583. Compound 3-1 Compound 3-1 was prepared by controlling the molar ratios of 3-(trithylthio)propanoic acid and diamine 2-2 as 2.4 in 65% yield. ¹H NMR (300 MHz, DMSO-d ₆): δ = 0.80–0.84 (m, 6 H), 1.21–1.30 (m, 8 H), 1.39 (d, J = 7.26 Hz, 3 H), 1.52 (m, 1 H), 2.37–2.50 (m, 8 H), 3.91–4.02 (m, 2 H), 4.43 (t, J = 7.08 Hz, 1 H), 7.06–7.34 (m, 30 H), 7.68 (d, J = 0.99 Hz, 2 H), 8.10 (s, 1 H), 8.75 (d, J = 6.78 Hz, 1 H), 10.10 (s, 2 H) ppm. ¹³C NMR (75 MHz, DMSO-d ₆): δ = 10.8, 10.9, 13.9, 16.6, 22.4, 23.1, 23.2, 27.3, 28.3, 29.7, 29.8, 35.1,38.2, 48.5, 66.1, 66.3, 112.7, 113.4, 126.7, 128.0, 129.1, 135.4, 139.2, 144.4, 166.7, 169.3, 172.7 ppm. ESI-HRMS: m/z calcd for C₆₂H₆₅N₃O₅S₂Na [M + Na]⁺: 1018.4263; found: 1018.4263. Compound 4-1 Compound 4-1 was prepared by controlling the molar ratios of 3-(trithylthio)propanoic acid and diamine 2-2 as 1.2 in 50% yield. ¹H NMR (300 MHz, DMSO-d ₆): δ = 0.78–0.83 (m, 6 H), 1.20–1.26 (m, 8 H), 1.33 (d, J = 7.26 Hz, 3 H), 1.50 (m, 1 H), 2.29–2.35 (m, 4 H), 3.85–4.02 (m, 2 H), 4.34 (t, J = 7.08 Hz, 1 H), 5.25 (s, 2 H), 6.65 (s, 1 H), 7.00 (s, 1 H), 7.05 (s, 1 H), 7.23–7.32 (m, 15 H), 8.50 (d, J = 6.54 Hz, 1 H), 9.74 (s, 1 H) ppm. ¹³C NMR (75 MHz, DMSO-d ₆): δ = 10.8, 13.9, 16.7, 22.4, 23.1, 27.5, 28.4, 29.8, 30.4, 35.1, 38.2, 48.4, 66.2, 106.7, 107.4, 108.3, 126.7, 128.0, 129.1, 135.5, 139.5, 144.38, 144.47. 148.9, 167.4, 168.9, 172.8 ppm. ESI-HRMS: m/z calcd for C₄₀H₄₇N₃O₄SNa [M + Na]⁺: 688.3185; found: 688.3179. Compound 4 ¹H NMR (300 MHz, DMSO-d ₆): δ = 0.80–0.84 (m, 6 H), 1.21–1.30 (m, 8 H), 1.38 (d, J = 7.26 Hz, 3 H), 1.50–1.52 (m, 1 H), 2.34–2.42 (m, 4 H), 3.92–4.04 (m, 4 H), 4.41 (m, 1 H), 7.23–7.37 (m, 15 H), 7.68 (s, 2 H), 8.09 (s, 1 H), 8.79 (d, J = 6.90 Hz, 1 H), 10.13 (s, 1 H), 10.54 (s, 1 H) ppm. ¹³C NMR (75MHz, DMSO-d ₆): δ = 10.8, 13.9, 16.6, 22.4, 23.1, 27.3, 28.3, 29.8, 38.2, 40.1, 48.5, 66.1, 66.3, 112.9, 113.5, 130.0, 126.7, 128.0, 129.1, 135.5, 138.7, 144.4, 164.8, 166.5, 169.3, 172.6 ppm. ESI-HRMS: m/z calcd for C₄₂H₄₈BrN₃O₅SNa [M + Na]⁺: 808.2396; found: 808.2374. Oligoamide 1a Light yellow powder (540 mg) in 70% yield. ¹H NMR (300 MHz, DMSO-d ₆): δ = 0.80–0.84 (m, 18 H), 1.21–1.30 (m, 24 H), 1.38 (d, J = 7.17 Hz, 9 H), 1.50–1.52 (m, 3 H), 2.35–2.42 (m, 8 H), 2.69–2.71 (m, 4 H), 2.92–2.94 (m, 4 H), 3.38 (s, 4 H), 3.92–4.01 (m, 6 H), 4.39–4.44 (m, 3 H), 7.24–7.33 (m, 30 H), 7.68–7.70 (m, 6 H), 8.11–8.13 (m, 3 H), 8.75–8.77 (m, 3 H), 10.10 (s, 2 H), 10.16 (s, 2 H), 10.26 (s, 2 H). ¹³C NMR (75 MHz, DMSO-d ₆): δ = 10.9, 13.9, 16.7, 22.4, 23.2, 27.4, 27.7, 28.3,29.8, 29.9, 35.1, 36.3, 38.3, 48.6, 66.2, 66.3, 112.7, 113.4, 126.8, 128.0, 129.1, 135.5, 139.3, 144.4, 166.7, 168.2, 169.3, 169.6, 172.7 ppm. ESI-HRMS: m/z calcd for C₁₀₈H₁₃₀N₉O₁₅S₄Na [M + Na]⁺: 1943.8467; found: 1943.8134. Oligoamide 1b Using 1a′ as starting material, light yellow powder (502 mg) in 85% yield. ¹H NMR (300 MHz, DMSO-d ₆): δ = 0.79–0.84 (m, 30 H), 1.21–1.30 (m, 40 H), 1.37 (d, J = 7.41 Hz, 15 H), 1.52 (m, 5 H), 2.34–2.39 (m, 8 H), 2.66–2.70 (m, 8 H), 2.91–2.93 (m, 8 H), 3.34 (s, 8 H), 3.99–4.01 (m, 10 H), 4.41–4.43 (m, 5 H), 7.22–7.34 (m, 30 H), 7.67–7.70 (m, 10 H), 8.10–8.13 (m, 5 H), 8.73–8.75 (m, 5 H), 10.08–10.25 (m, 10 H) ppm. ¹³C NMR (75 MHz, DMSO-d ₆): δ = 10.8, 10.9, 13.9, 16.7, 22.4, 23.2, 27.6, 28.3, 29.8, 29.9, 36.2, 38.3, 48.5, 66.2, 66.3, 112.7, 113.4, 113.6, 126.7, 128.0, 129.1, 135.5, 139.2, 139.3, 144.4, 166.7, 168,2, 169.3, 169.6, 169.7, 172.7 ppm. ESI-HRMS: m/z calcd for C₁₅₄H₁₉₆N₁₅O₂₅S₆Na₂ [M + 2Na – H]⁺: 2893.2646; found: 2893.2623. Oligoamide 1c Using 1b′ as starting material, light yellow powder (301 mg) in 63% yield. ¹H NMR (300 MHz, DMSO-d ₆): δ = 0.80–0.84 (m, 42 H), 1.12–1.30 (m, 56 H), 1.38 (d, J = 7.20 Hz, 21 H), 1.51 (m, 7 H), 2.34–2.40 (m, 8 H), 2.66–2.71 (m, 12 H), 2.91–2.96 (m, 12 H), 3.35 (s, 12 H), 3.92–4.01 (m, 14 H), 4.39–4.41 (m, 7 H), 7.22–7.36 (m, 30 H), 7.67–7.70 (m, 14 H), 8.10–8.13 (m, 7 H), 8.75–8.78 (m, 7 H), 10.09–10.26 (m, 14 H) ppm. ¹³C NMR (75 MHz, DMSO-d ₆): δ = 10.8, 10.9, 13.9, 16.7, 22.4, 23.2, 23.3, 27.3, 27.6, 28.4, 29.8, 29.9, 35.1, 35.4, 36.2, 38.2, 38.3, 48.6, 66.2, 66.3, 112.7, 113.4, 113.6, 126.8, 128.1, 129.1, 135.5, 139.2, 139.3, 144.4, 166.8, 168,3, 169.3, 169.6, 169.7, 172.7 ppm. ESI-HRMS: m/z calcd for C₂₀₀H₂₆₂N₂₁O₃₅S₈KNa [M + Na + K – H]⁺: m/z 3835.6668; found: 3835.6474. Oligoamide 1d Using 1c′ as starting material, light yellow powder (43 mg) in 77% yield. ¹H NMR (300 MHz, DMSO-d ₆): δ = 0.80–0.84 (m, 54 H), 1.12–1.30 (m, 72 H), 1.38 (d, J = 7.23 Hz, 27 H), 1.50–1.52 (m, 9 H), 2.34–2.40 (m, 8 H), 2.66–2.71 (m, 16 H), 2.92–2.96 (m, 16 H), 3.35 (s, 16 H), 3.92–4.01 (m, 18 H), 4.39–4.44 (m, 9 H), 7.24–7.37 (m, 30 H), 7.67–7.71 (m, 18 H), 8.10–8.13 (m, 9 H), 8.75–8.78 (m, 9 H), 10.1–10.3 (m, 18 H) ppm. ¹³C NMR (75 MHz, DMSO-d ₆): δ = 11.2, 11.3, 14.3, 17.1, 22.8, 23.6, 23.7, 27.7, 28.1, 28.7, 28.8, 30.2, 30.3, 35.6, 35.8, 36.7, 38.6, 38.7, 49.0, 66.6, 66.8, 113.2, 113.8, 114.1, 127.2, 128.5, 129.5, 135.9, 139.6, 139.7, 144.9, 167.2, 168.6, 169.7, 170.1, 173.1 ppm. ESI-HRMS: m/z calcd for C₂₄₇H₃₂₉Cl₂N₂₇O₄₅S₁₀ [M + CH₂Cl₂ – 2H]^2–: 2392.555; found: 2392.8. Representative Procedure for the Preparation of Oligoamide 1a The solution of compound 4 (802 mg, 1.02 mmol) dissolved in CH₂Cl₂ (10 mL) was added dropwise to the ice-cold mixture of compound 3 (209 mg, 0.409 mmol) and Et₃N(0.14 mL, 1.02 mmol) in CH₂Cl₂ (20 mL). The mixture was allowed to warm to r.t. and kept at this temperature overnight. The resulting mixture was washed with 1 M HCl solution (30 mL), brine (30 mL), and then dried over anhydrous Na₂SO₄. After filtration and concentration the crude product was purified by column chromatography (3 vol% MeOH in CH₂Cl₂, R_f = 0.1) to afford pure compound 1a. Oligoamides 1b–d could be prepared using the same method described as 1a. Representative Procedure for the Preparation of Oligoamide 1a′ The solution of TFA (0.31 mL, 4.16 mmol) in CH₂Cl₂ (10 mL) was added dropwise to the ice-cold mixture of compound 1a (400 mg, 0.208 mmol) and triethylsilane (0.33 mL, 2.08 mmol) in CH₂Cl₂ (20 mL) over 15 min. The mixture was allowed to warm to r.t. and kept at this temperature for 1 h. After concentration, the crude mixture was purified by flash column chromatography (5% v/v MeOH in CH₂Cl₂, R_f = 0.2) to give compound 1a′. Oligoamides 1b′ and 1c′ could be prepared using the same method described as 1a′. Oligoamide 1a′ White solid; yield: 293 mg (98%). Oligoamide 1b′ White solid; yield: 289 mg (97%). Oligoamide 1c′ White solid; yield: 38 mg (97%).

Supplementary Material

Supporting Information (PDF)