Odorless Eco-Friendly Synthesis of Thio- and Selenoglycosides in Ionic Liquid

Abstract

An environmentally benign odorless methodology for the preparation of 1,2-trans-thio- and selenoglycosides is reported. In a one-pot condition, the reductive cleavage of disulfides and di­selenides using triethylsilane and borontrifluoride diethyletherate combination followed by the reaction of the in situ generated ­thiolate and selenoetes with glycosyl acetate derivatives in recyclable room-temperature ionic liquid, [BMIM]˙BF₄ resulted in excellent yields of thio- and selenoglycosides avoiding the use of obnoxious thiols/selenols and metallic catalysts.

thioglycoside - selenoglycoside - disulfide - diselenide - triethylsilane - ionic liquid

References and Notes

1a Oscarson S. In Carbohydrates in Chemistry and Biology   Vol. 1:  Ernst B. Hart GW. Sinay P. Wiley-VCH; Weinheim: 2000.  p.93-116  

1b Nicolaou KC. Ueno H. In Preparative Carbohydrate Chemistry   Hanessian S. Marcel Dekker; New York: 1997.  p.313-338  

2a Tsai TYR. Jin H. Wiesner K. Can. J. Chem.  1984,  62:  1403 

2b Wuts PGM. Bigelow SS. J. Org. Chem.  1983,  48:  3489 

2c Lear MJ. Yoshimura F. Hirama M. Angew. Chem. Int. Ed.  2001,  40:  946 

2d Nicolaou KC. Dolle RE. Papahatjis DP. Randall JL. J. Am. Chem. Soc.  1984,  106:  4189 

2e Dolle RE. Nicolaou KC.
J. Am. Chem. Soc.  1985,  107:  1691 

2f Nicolaou KC. Bockovich NJ. Carcanague DR. Hummel CW. Even LF. J. Am. Chem. Soc.  1992,  114:  8701 

3a Codee JDC. Litjens REJN. van den Bos LJ. Overkleeft HS. van der Marel GA. Chem. Soc. Rev.  2005,  34:  769 

3b Garegg PJ. Adv. Carbohydr. Chem. Biochem.  1997,  52:  179 

3c Fugedi P. Garegg PJ. Lohn H. Norberg T. Glycoconjugate J.  1987,  4:  97 

3d Toshima K. Tatsuta K. Chem. Rev.  1993,  93:  1503 

3e Ferrier RJ. Furneaux RH. Methods Carbohydr. Chem.  1980,  8:  251 

3f Kartha KPR. Field RA. In Best Synthetic Methods: Carbohydrates   Osborn HMI. Academic Press; Oxford: 2003.  p.121-145  

4a Rosenbrook W. Riley DA. Lartey PA. Tetrahedron Lett.  1985,  26:  3 

4b Posner GH. Haines SR. Tetrahedron Lett.  1985,  26:  5 

4c Nicolaou KC. Dolle RE. Papahatjis DP. Randall LJ. J. Chem. Soc., Chem. Commun.  1984,  1155 

5a Kahne D. Walker S. Cheng Y. van Engen D. J. Am. Chem. Soc.  1989,  111:  6881 

5b Raghavan S. Kahne D.
J. Am. Chem. Soc.  1993,  115:  1580 

5c Yan L. Kahne D. J. Am. Chem. Soc.  1996,  118:  9239 

5d Crich D. Sun S.
J. Org. Chem.  1997,  62:  1198 

6a Brown DS. Ley SV. Vile S. Tetrahedron Lett.  1988,  29:  4873 

6b Brown DS. Ley SV. Vile S. Thompson M. Tetrahedron  1991,  47:  1329 

6c Chang GX. Lowary TL. Org. Lett.  2000,  2:  1505 

6d Vlahov IR. Vlahova PI. Linhardt RJ. J. Am. Chem. Soc.  1997,  119:  1480 

7a Khan SH. Hindsgaul O. In Molecular Glycobiology   Fukuda M. Hindsgaul O. IRL; Oxford: 1994.  p.206 

7b Norberg T. In Modern Methods in Carbohydrate Synthesis, Frontiers in Natural Product Research Series   Vol. 1:  Khan SH. O’Neill RA. Harwood Academic Publishers; Amsterdam: 1995.  p.82-106  

8a Varki A. Glycobiology  1993,  3:  97 

8b Witczak ZJ. Curr. Med. Chem.  1999,  6:  165 

9 Kanie O. Ito Y. Ogawa T. J. Am. Chem. Soc.  1994,  116:  12073 

10a Ferrier RJ. Hay RW. Vethaviyasar N. Carbohydr. Res.  1973,  27:  55 

10b Lemieux RU. Can. J. Chem.  1951,  29:  1079 

10c Lönn H. Carbohydr. Res.  1985,  139:  105 

10d Das SK. Roy N. Carbohydr. Res.  1996,  296:  1079 

10e Kihlberg JO. Leigh DA. Bundle DR. J. Org. Chem.  1990,  55:  2860 

10f Agnihotri G. Tiwari P. Misra AK. Carbohydr. Res.  2005,  340:  1393 

10g Tai CA. Kulkarni SS. Hung SC. J. Org. Chem.  2003,  68:  8719 

10h Weng SS. Lin YD. Chen CT. Org. Lett.  2006,  8:  5633 

11a Hanessian S. Guindon Y. Carbohydr. Res.  1980,  86:  C3 

11b Pozsgay V. Jennings HJ. Tetrahedron Lett.  1987,  28:  1375 

11c Kameyama A. Ishida H. Kiso M. Hasegawa A. J. Carbohydr. Chem.  1991,  10:  549 

12a Mukherjee C. Tiwari P. Misra AK. Tetrahedron Lett.  2006,  47:  441 

12b Zhao X. Yu Z. Yan S. Wu S. Liu R. He W. Wang L. J. Org. Chem.  2005,  70:  7338 

13a Tiwari P. Agnihotri G. Misra AK. J. Carbohydr. Chem.  2005,  24:  723 

13b Ibatullin FM. Shabalin KA. Janis JV. Shavva AG. Tetrahedron Lett.  2003,  44:  7961 

14a Randell KD. Johnston BD. Brown PN. Pinto BM. Carbohydr. Res.  2000,  325:  253 

14b Jiaang W.-T. Chang M.-Y. Tseng P.-H. Chen S.-T. Tetrahedron Lett.  2000,  41:  3127 

15a Mehta S. Pinto BM. J. Org. Chem.  1993,  58:  3269 

15b Mehta S. Pinto BM. Tetrahedron Lett.  1991,  32:  4435 

16a Crich D. Suk D.-H. Sun S. Tetrahedron: Asymmetry  2003,  14:  2861 

16b Witczak ZJ. Whistler RL. Heterocycles  1982,  19:  1719 

17a Gerz M. Matter H. Kessler H. Angew. Chem., Int. Ed. Engl.  1993,  32:  269 

17b Aloui M. Chambers DJ. Cumpstey I. Fairbanks AJ. Redgrave AJ. Seward CMP. Chem. Eur. J.  2002,  8:  2608 

18a Debenham SD. Toone EJ. Tetrahedron: Asymmetry  2000,  11:  385 

18b Aravind A. Baskaran S. Tetrahedron Lett.  2005,  46:  743 

18c Aravind A. Mohanty SK. Pratap TV. Baskaran S. Tetrahedron Lett.  2005,  46:  2965 

19a Jain N. Kumar A. Chauhan S. Chauhan SMS. Tetrahedron  2005,  61:  1015 

19b Murugesan S. Linhardt RJ. Curr. Org. Synth.  2005,  2:  437 

20a Pakulski Z. Synthesis  2003,  2074 

20b Galan MC. Jouvin K. Alvarez-Dorta D. Carbohydr. Res.  2010,  345:  45 

20c Park T.-J. Weiwer M. Yuan X. Baytas SN. Munoz EV. Murugesan S. Linhardt RJ. Carbohydr. Res.  2007,  342:  614 

20d Rencurosi A. Lay L. Russo G. Caneva E. Poletti L. J. Org. Chem.  2005,  70:  7765 

20e Forsyth SA. MacGarlane DR. Thomson RJ. von Itzstein M. Chem. Commun.  2002,  714 

20f Zhang J. Ragauskas AJ. Carbohydr. Res.  2005,  340:  2812 

21 Dasgupta F. Garegg PJ. Acta Chem. Scand.  1989,  43:  471 

22 Mukherjee CM. Misra AK. J. Carbohydr. Chem.  2007,  26:  213 

23 Martin-Lomas M. Khiar N. Garcia S. Koessler J.-L. Nieto PM. Rademacher TW. Chem. Eur. J.  2000,  6:  3608 

24 Khiar N. Martin-Lomas M. J. Org. Chem.  1995,  60:  7017 

25 Pozsgay V. Jennings HJ. J. Org. Chem.  1988,  53:  4042 

26 Chowdhury US. Tetrahedron  1996,  52:  12775 

27 Tropper FD. Andersson FO. Grand-Maitre C. Roy R. Synthesis  1991,  734 

28 Tiwari P. Misra AK. Tetrahedron Lett.  2006,  47:  2345 

29

Spectral data of products, which have not been reported earlier, are presented below.

p -Nitrophenyl 2,3,4,6-Tetra- O -acetyl-1-thio-β- d -glucopyranoside (16)
Yellow solid; mp 180-182 ˚C; [α]_D -32.7 (c 1.2, CHCl₃). IR (KBr): 2923, 2368, 1753, 1344, 1220, 1042, 770 cm^-¹. ^¹H NMR (200 MHz, CDCl₃): δ = 8.16 (d, J = 8.9 Hz, 2 H), 7.59 (d, J = 8.8 Hz, 2 H), 5.28 (t, J = 9.2 Hz each, 1 H, H-3), 5.08 (t, J = 9.7 Hz each, 1 H, H-2), 5.04 (t, J = 9.6 Hz each, 1 H, H-4), 4.89 (d, J = 10.0 Hz, 1 H, H-1), 4.25-4.21 (m, 2 H, H-6_a,b), 3.85-3.80 (m, 1 H, H-5), 2.10, 2.08, 2.04, 2.0 (4 s, 12 H, 4 COCH₃). ^¹³C NMR (50 MHz, CDCl₃): δ = 170.2, 169.9, 169.2, 169.0, 147.6, 141.6, 131.7 (2 C), 124.1 (2 C), 84.6, 76.6, 74.0, 70.0, 68.3, 62.2, 21.0, 20.9, 20.8 (2 C). ESI-MS: m/z = 508.1 [M + Na]⁺. Anal. Calcd for C₂₀H₂₃NO₁₁S (485.10): C, 49.48; H, 4.78. Found: C, 49.25; H, 5.0.
Benzyl 2,3,4,6-Tetra- O -acetyl-1-seleno-β- d -gluco-pyranoside (31)
Yellow oil; [α]_D ^²5 -30 (c 1.5, CHCl₃). IR (neat): 2934, 1769, 1357, 1242, 1074, 764 cm^-¹. ^¹H NMR (300 MHz, CDCl₃):
δ = 7.40-7.21 (m, 5 H, ArH), 5.88 (d, J = 8.5 Hz, 1 H), 5.27 (t, J = 9.5 Hz each, 1 H), 5.06-4.89 (m, 2 H), 4.34-4.19 (m, 2 H), 3.90 (d, J = 11.1 Hz, 1 H), 3.83-3.67 (ABq, J = 12.0 Hz, 2 H), 2.08, 2.02, 1.99 (3 s, 12 H, 4 COCH ₃). ^¹³C NMR (50 MHz, CDCl₃): δ = 171.0, 170.8, 169.9 (2 C), 135.0-127.0 (ArC), 78.8, 76.3, 71.7, 71.2, 69.9, 68.6, 62.0, 26.6, 21.0, 20.9 (2 C). ESI-MS: m/z = 525.0 [M + Na]⁺. Anal. Calcd for C₂₁H₂₆O₉Se (502.07): C, 50.31; H, 5.23. Found: C, 50.08; H, 5.50.
Benzyl 2,3,4,6-Tetra- O -acetyl-1-seleno-α- d -manno-pyranoside (33)
Yellow oil; [α]_D ^²5 +126.8 (c 1.0, CHCl₃). IR (neat): 2972, 2362, 1742, 1598, 1373, 1246, 1107, 1050, 977, 756 cm^-¹. ^¹H NMR (200 MHz, CDCl₃): δ = 7.28-7.09 (m, 5 H, ArH), 5.35 (br s, 1 H, H-2), 5.24 (br s, 1 H, H-1), 5.20-5.16 (m, 2 H, H-3 and H-4), 4.24-4.20 (m, 2 H, H-6_ab), 3.91-3.85 (m, 1 H, H-5), 3.77-3.73 (ABq, J = 12.0 Hz, 2 H, CH₂Ph), 2.07, 2.03, 1.98, 1.90 (4 s, 12 H, 4 COCH₃). ^¹³C NMR (50 MHz, CDCl₃): δ = 170.2, 169.4 (2 C), 169.3, 137.6, 128.6 (2 C), 128.3 (2 C), 126.8, 77.6, 71.4, 70.6, 69.7, 65.8, 61.8, 27.4, 20.5, 20.4, 20.3, 20.2. ESI-MS: m/z = 525 [M + Na]⁺. ESI-MS: m/z = 525.0 [M + Na]⁺. Anal. Calcd for C₂₁H₂₆O₉Se (502.07): C, 50.31; H, 5.23. Found: C, 50.09; H, 5.52.
Benzyl 2,3,4-Tri- O -acetyl-1-seleno-α- l -rhamno-pyranoside (36) Yellow oil; [α]_D ^²5 -114 (c 1.2, CHCl₃). IR (neat): 2367, 1756, 1600, 1366, 1230, 955 cm^-¹. ^¹H NMR (200 MHz, CDCl₃): δ = 7.28-7.14 (m, 5 H, ArH), 5.34 (br s, 1 H, H-1), 5.32-5.30 (m, 1 H, H-2), 5.18 (dd, J = 9.7, 3.0 Hz, 1 H, H-3), 5.04 (t, J = 9.7 Hz each, 1 H, H-4), 4.12-4.02 (m, 1 H, H-5), 3.83 (ABq, J = 12.2 Hz, 2 H, PhCH₂), 2.08, 2.01, 1.93 (3 s, 9 H, 3 COCH₃), 1.18 (d, J = 6.2 Hz, 1 H, CCH₃). ESI-MS: m/z = 467.0 [M + Na]⁺. Anal. Calcd for C₁₉H₂₄O₇Se (444.07): C, 51.47; H, 5.46. Found: C, 51.25; H, 5.70.
Benzyl 2,3,4,6-Tetra- O -acetyl-α- d -glucopyranosyl-(1→4)-2,3,6-tri- O -acetyl-1-seleno-β- d -glucopyranoside (39) Yellow oil; [α]_D ^²5 +51 (c 1.0, CHCl₃). IR (neat): 3023, 1764, 1418, 1257, 1086, 769 cm^-¹. ^¹H NMR (400 MHz, CDCl₃):
δ = 7.32-7.20 (m, 5 H, ArH), 5.40-5.23 (m, 2 H), 5.18-5.09 (m, 1 H), 5.06-4.88 (m, 2 H), 4.86-4.76 (m, 1 H), 4.54-4.49 (m, 1 H), 4.46-4.38 (m, 1 H), 4.26-4.16 (m, 2 H), 4.06-3.82 (m, 5 H), 3.58-3.49 (m, 1 H), 2.13, 2.07, 1.99, 1.96, 1.95, 1.94 (6 s, 21 H, 7 COCH₃). ESI-MS: m/z = 813.1 [M + Na]⁺. Anal. Calcd for C₃₃H₄₂O₁₇Se (790.16): C, 50.19; H, 5.36. Found: C, 50.0; H, 5.60.
Phenyl 2,3,4,6-Tetra- O -acetyl-β- d -galactopyranosyl-(1→4)-2,3,6-tri- O -acetyl-1-seleno-β- d -glucopyranoside (40)
Yellow oil; [α]_D ^²5 +9 (c 1.0, CHCl₃). IR (neat): 3036, 1790, 1432, 1276, 1094, 766 cm^-¹. ^¹H NMR (400 MHz, CDCl₃):
δ = 7.56-7.26 (m, 5 H, ArH), 5.30-5.28 (m, 1 H), 5.16 (t, J = 9.1 Hz each, 1 H), 5.05 (dd, J = 7.3 Hz each, 1 H), 4.94-4.82 (m, 3 H), 4.51-4.46 (m, 1 H), 4.42 (d, J = 7.9 Hz, 1 H), 4.12-4.02 (m, 3 H), 3.85-3.81 (m, 1 H), 3.70 (t, J = 9.1 Hz each, 1 H), 3.62-3.56 (m, 1 H), 2.13, 2.07, 2.05, 2.01, 2.0, 1.94 (6 s, 21 H, 7 COCH₃). ESI-MS: m/z = 799.1 [M + Na]⁺. Anal. Calcd for C₃₂H₄₀O₁₇Se (776.14): C, 49.55; H, 5.20. Found: C, 49.32; H, 5.50.

Benzyl 2,3,4,6-Tetra- O -acetyl-β- d -galactopyranosyl-(1→4)-2,3,6-tri- O -acetyl-1-seleno-β- d -glucopyranoside (41)
Yellow oil; [α]_D ^²5 +21 (c 1.0, CHCl₃). IR (neat): 3023, 1767, 1424, 1281, 1089, 769 cm^-¹. ^¹H NMR (400 MHz, CDCl₃):
δ = 7.30-7.27 (m, 5 H, ArH), 5.40-5.28 (m, 2 H), 5.20-4.88 (m, 4 H), 4.54-4.44 (m, 2 H), 4.22-4.06 (m, 4 H), 4.02-3.86 (m, 2 H), 3.82-3.70 (m, 1 H), 3.56-3.48 (m, 1 H), 2.17, 2.15, 2.14, 2.06, 2.03, 2.0, 1.97 (7 s, 21 H, 7 COCH₃). ESI-MS: m/z = 813.1 [M + Na]⁺. Anal. Calcd for C₃₃H₄₂O₁₇Se (790.16): C, 50.19; H, 5.36. Found: C, 50.0; H, 5.58.