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Synlett 2020; 31(11): 1087-1093
DOI: 10.1055/s-0040-1707098
DOI: 10.1055/s-0040-1707098
letter
Copper-Catalyzed Stereoselective Synthesis of 2-Deoxygalactosides
The project was financially supported by Natural Science Foundation of Shanghai (11ZR1410400) and by the Large Instruments Open Foundation of East China Normal University (20162015).Further Information
Publication History
Received: 14 January 2020
Accepted after revision: 03 April 2020
Publication Date:
05 May 2020 (online)
Abstract
An efficient glycosylation method to synthesize 2-deoxy-O-galactosides based on a Cu(II)-catalyzed reaction without additional ligand has been developed. The glycosylation was amenable to different protected glycal donors and a wide range of acceptors including alcohols, amino acids, sugars, and phenol, and proceeds with excellent yield and high α-selectivity under mild conditions. The reaction proceeds readily on a gram scale, and its versatility is exemplified in the synthesis of oligosaccharides.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707098.
- Supporting Information
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References and Notes
- 1a McCranie EK, Bachmann BO. Nat. Prod. Rep. 2014; 31: 1026
- 1b Daniel PT, Koert U, Schuppan J. Angew. Chem. Int. Ed. 2006; 45: 872
- 1c He XM, Liu HW. Curr. Opin. Chem. Biol. 2002; 6: 590
- 1d Gao J, Guo Z. Med. Res. Rev. 2018; 38: 556
- 1e Zhang XT, Gu ZY, Liu L, Wang S, Xing GW. Chem. Commun. 2015; 51: 8606
- 2a Yadav JS, Reddy BV. S, Reddy KB, Satyanarayana M. Tetrahedron Lett. 2002; 43: 7009
- 2b Elshahawi SI, Shaaban KA, Kharel MK, Thorson JS. Chem. Soc. Rev. 2015; 44: 7591
- 3a Hou D, Lowary TL. Carbohydr. Res. 2009; 344: 1911
- 3b Zeng J, Xu Y, Meng Q. Sci. China. Chem. 2017; 60: 1162
- 3c Bennett CS, Galan MC. Chem. Rev. 2018; 118: 7931
- 4a Thiem J, Gerken M. J. Org. Chem. 1985; 50: 954
- 4b Roush WR, Bennett CE. J. Am. Chem. Soc. 1999; 121: 3541
- 4c Blanchard N, Roush WR. Org. Lett. 2003; 5: 81
- 5a Roush WR, Gung BW, Bennett CE. Org. Lett. 1999; 1: 891
- 5b Hou D, Lowary TL. J. Org. Chem. 2009; 74: 2278
- 5c Bandi R, Chalapala S, Chandrasekaran S. Org. Biomol. Chem. 2018; 16: 2248
- 6a Gillard JW, Israel M. Tetrahedron Lett. 1981; 22: 513
- 6b Verma VP, Wang CC. Chem. Eur. J. 2013; 19: 846
- 6c Zhang W, Luo X, Wang Z, Zhang J. J. Carbohydr. Chem. 2016; 35: 315
- 6d Wever WJ, Cinelli MA, Bowers AA. Org. Lett. 2013; 15: 30
- 6e Kaneko M, Herzon SB. Org. Lett. 2014; 16: 2776
- 6f Qiu S, Sun G, Ding Z, Chen H, Zhang J. Synlett 2017; 28: 2024
- 7 Balmond EI, Coe DM, Galan MC, McGarrigle EM. Angew. Chem. Int. Ed. 2012; 51: 9152
- 8a Balmond EI, Benito-Alifonso D, Coe DM, Alder RW, McGarrigle EM, Galan MC. Angew. Chem. Int. Ed. 2014; 53: 8190
- 8b Sau A, Williams R, Palo-Nieto C, Franconetti A, Medina S, Galan MC. Angew. Chem. Int. Ed. 2017; 56: 3640
- 9 Palo-Nieto C, Sau A, Galan MC. J. Am. Chem. Soc. 2017; 139: 14041
- 10 Sherry BD, Loy RN, Toste FD. J. Am. Chem. Soc. 2004; 126: 4510
- 11 Zhao G, Wang T. Angew. Chem. Int. Ed. 2018; 57: 6120
- 12a Das S, Pekel D, Neudçrfl J, Berkessel A. Angew. Chem. Int. Ed. 2015; 54: 12479
- 12b Palo-Nieto C, Sau A, Williams R, Galan MC. J. Org. Chem. 2017; 82: 407
- 13 Bradshaw GA, Colgan AC, Allen NP, Pongener I, Boland MB, Ortin Y, McGarrigle EM. Chem. Sci. 2019; 10: 508
- 14 Cui XK, Zhong M, Meng XB, Li ZJ. Carbohydr. Res. 2012; 358: 19
- 15a Yang GF, Wang QB, Luo XS, Zhang JB, Tang J. Glycoconj. J. 2012; 29: 453
- 15b Yang GF, Luo XS, Guo H, Wang QB, Zhou JF, Huang TY, Tang J, Shan JJ, Zhang JB. J. Carbohydr. Chem. 2018; 37: 128
- 15c Qiu SF, Zhang W, Sun GS, Wang ZF, Zhang JB. ChemistrySelect 2016; 1: 4840
- 16a Sau AT, Palo-Nieto C, Galan MC. J. Org. Chem. 2019; 84: 2415
- 16b Singh AK, Venkatesh R, Kandasamy J. Synthesis 2019; 51: 4215
- 16c Mishra KB, Kandasamy J. Asian J. Org. Chem. 2019; 8: 549
- 16d Singh AK, Kandasamy J. Org. Biomol. Chem. 2018; 16: 5107
- 17 Thomba RS, Jadhav VH. RSC Adv. 2016; 6: 30846
- 18a Tai C.-A, Kulkarni SS, Hung S.-C. J. Org. Chem. 2003; 68: 8719
- 18b Kusunuru AK, Tatina M, Yousuf SK, Mukherjee D. Chem. Commun. 2013; 49: 10154
- 18c Srinivas B, Reddy TR, Krishna PR, Kashyap S. Synlett 2014; 25: 1325
- 18d Joseph R, Dyer FB, Garner P. Org. Lett. 2013; 15: 732
- 18e Wang HY, Simmons CJ, Blaszczyk SA, Balzer PG, Luo R, Duan X, Tang W. Angew. Chem. Int. Ed. 2017; 56: 15698
- 18f Verdelet T, Benmahdjoub S, Benmerad B, Alami M, Messaoudi S. J. Org. Chem. 2019; 84: 9226
- 18g Xu QC, Gu ZY, Xing GW. Tetrahedron 2017; 73: 2123
- 19 Zhou J, Chen H, Shan J, Li J, Yang G, Chen X, Xin K, Zhang J, Tang J. J. Carbohydr. Chem. 2014; 33: 313
- 20 Guo H, Si W, Li J, Yang G, Tang T, Wang Z, Tang J, Zhang J. Synthesis 2019; 51: 2984
- 21 Dong YX, Ding ZK, Guo H, Zhou L, Jiang N, Chen HS, Qiu SF, Xu X, Zhang J. Synlett 2019; 30: 1419
- 22 Ding ZK, Luo XS, Ma Y, Chen HS, Qiu SF, Sun GS, Zhang W, Yu C, Wu Z, Zhang J. J. Carbohydr. Chem. 2018; 37: 81
- 23 Capozzi G, Falciani C, Menichetti S, Nativi C, Raffaelli B. Chem. Eur. J. 1999; 5: 1748
- 24 Paul S, Jayaraman N. Carbohydr. Res. 2007; 342: 1305
- 25 Tatina MB, Moussa Z, Xia MX, Judeh ZM. A. Chem. Commun. 2019; 55: 12204
- 26 Sletten ET, Tu YJ, Schlegel HB, Nguyen HM. ACS Catal. 2019; 9: 2110
- 27 6-O-(3’,4’,6’-Tri-O-benzyl-2’-deoxy-α-d-galactopyranosyl)-1,2:3,4-di-O-isopropylidene-α-d-galactopyranoside (3g)Under a nitrogen atmosphere, glycal donor 1a (0.10 mmol, 41.6 mg) and nucleophile acceptor 2g (0.12 mmol, 31.2 mg) were dissolved in anhydrous DCM (1.0 mL). Meanwhile CuBr2 (0.005 mmol, 1.3 mg) was added to the system quickly. The reaction mixture was stirred at 25 °C until the reaction was determined to be complete by TLC. The reaction was then quenched with sat. aq. NaHCO3, and the mixture was extracted with DCM. The combined organic phases were washed with sat. aq. NaHCO3 and brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (PE/EtOAc = 6:1) to give a yellow syrup. Yield: 55.4 mg (82%), α:β >30:1. Trichloroethyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3c) Yield: 46.2 mg (82%); colorless syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.39–7.26 (m, 15 H), 5.24 (d, J = 2.3 Hz, 1 H), 4.95 (d, J = 11.6 Hz, 1 H), 4.62 (d, J = 11.4 Hz, 3 H), 4.51 (d, J = 11.8 Hz, 1 H), 4.44 (d, J = 11.8 Hz, 1 H), 4.19 (d, J = 11.5 Hz, 1 H), 4.07 (d, J = 11.5 Hz, 1 H), 4.04–3.98 (m, 2 H), 3.96 (s, 1 H), 3.59 (d, J = 6.3 Hz, 2 H), 2.29 (td, J = 12.5, 3.4 Hz, 1 H), 2.16 (dd, J = 12.7, 4.2 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 138.81, 138.39, 138.09, 128.52, 128.50, 128.34, 128.34, 127.82, 127.70, 127.68, 127.53, 98.87, 96.85, 79.15, 74.43, 73.55, 72.90, 71.03, 70.69, 69.46, 30.73. HRMS (ESI): m/z [M + Na]+ calcd for C29H31Cl3NaO5: 587.1129; found: 587.1110. Furfuraldehyde-5-methyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3e) Yield: 48.2 mg (89%); yellow syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 9.61 (s, 1 H), 7.36–7.26 (m, 15 H), 7.17 (d, J = 3.5 Hz, 1 H), 6.48 (d, J = 3.5 Hz, 1 H), 5.08 (d, J = 3.1 Hz, 1 H), 4.94 (d, J = 11.6 Hz, 1 H), 4.66–4.58 (m, 4 H), 4.56–4.42 (m, 3 H), 3.96–3.90 (m, 3 H), 3.61–3.54 (m, 2 H), 2.26 (td, J = 12.6, 3.6 Hz, 1 H), 2.04 (dd, J = 12.8, 4.3 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 177.84, 157.96, 152.84, 138.85, 138.51, 138.11, 128.49, 128.31, 127.88, 127.81, 127.63, 127.37, 111.63, 97.69, 74.60, 74.39, 73.58, 72.93, 70.58, 70.48, 69.59, 60.96, 30.93. HRMS (ESI): m/z [M + Na]+ calcd for C33H34NaO7: 565.2197; found: 565.2196. N-(9-fluorenylmethoxycarbonyl)-L-serine methyl ester-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3f)Yield: 70.4 mg (93%); yellow syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.76 (d, J = 7.6 Hz, 2 H), 7.58 (d, J = 7.4 Hz, 2 H), 7.41–7.26 (m, 19 H), 5.91 (d, J = 8.7 Hz, 1 H), 4.94 (dd, J = 14.2, 7.0 Hz, 2 H), 4.64–4.56 (m, 3 H), 4.56–4.45 (m, 2 H), 4.43–4.32 (m, 3 H), 4.21 (t, J = 7.1 Hz, 1 H), 3.99 (dd, J = 10.8, 3.7 Hz, 1 H), 3.93–3.83 (m, 4 H), 3.75 (s, 3 H), 3.62–3.57 (m, 1 H), 3.56–3.51 (m, 1 H), 2.23 (td, J = 12.4, 3.4 Hz, 1 H), 1.96 (dd, J = 12.5, 3.9 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 170.81, 156.09, 143.91, 141.36, 138.79, 138.40, 138.03, 128.60, 128.21, 128.05, 127.53, 127.46, 127.13, 125.19, 120.04, 99.22, 74.38, 73.49, 72.82, 70.55, 69.58, 68.77, 67.18, 54.56, 52.63, 47.19, 31.12. HRMS (ESI): m/z [M + Na]+ calcd for C46H47NNaO9: 780.3143; found: 780.3127. 4-t-Butyl-Phenyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3k) Yield: 47.0 mg (83%); yellow syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.41–7.26 (m, 15 H), 7.24 (d, J = 7.2 Hz, 2 H), 7.00 (d, J = 8.7 Hz, 2 H), 5.69 (d, J = 2.9 Hz, 1 H), 4.98 (d, J = 11.5 Hz, 1 H), 4.70–4.64 (m, 3 H), 4.43 (d, J = 11.6 Hz, 1 H), 4.37 (d, J = 11.6 Hz, 1 H), 4.15 (dd, J = 11.1, 3.2 Hz, 1 H), 4.09 (t, J = 6.5 Hz, 1 H), 4.03 (s, 1 H), 3.70–3.64 (m, 1 H), 3.56 (dd, J = 9.3, 5.7 Hz, 1 H), 2.40 (td, J = 12.4, 3.6 Hz, 1 H), 2.21 (dd, J = 12.7, 4.4 Hz, 1 H), 1.30 (s, 9 H). 13C NMR (125 MHz, CDCl3): δ = 154.83, 144.65, 138.92, 138.57, 138.15, 128.52, 128.39, 128.3, 127.85, 127.69, 127.66, 127.62, 127.43, 126.26, 116.15, 96.82, 74.73, 74.51, 73.42, 72.98, 70.65, 69.32, 34.21, 31.59, 31.43. HRMS (ESI): m/z [M + Na]+ calcd for C37H42NaO5: 589.2924; found: 589.2916. 4-Fluoro-Phenyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3m) Yield: 41.7 mg (79%); colorless syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.42–7.19 (m, 15 H), 7.01 (dd, J = 8.7, 4.4 Hz, 2 H), 6.93 (t, J = 8.5 Hz, 2 H), 5.62 (s, 1 H), 4.97 (d, J = 11.5 Hz, 1 H), 4.71–4.61 (m, 3 H), 4.43 (d, J = 11.6 Hz, 1 H), 4.37 (d, J = 11.6 Hz, 1 H), 4.12 (d, J = 11.6 Hz, 1 H), 4.04 (dd, J = 15.5, 9.2 Hz, 2 H), 3.67–3.60 (m, 1 H), 3.55 (dd, J = 9.2, 6.1 Hz, 1 H), 2.39 (dd, J = 12.4, 3.1 Hz, 1 H), 2.20 (dd, J = 12.7, 4.1 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 159.05, 157.14, 153.08, 138.83, 138.48, 138.06, 128.55, 128.43, 128.36, 128.32, 127.79, 127.77, 127.72, 127.68, 127.44, 118.14, 118.08, 115.94, 115.76, 97.36, 74.56, 74.51, 73.45, 72.93, 70.80, 70.66, 69.40, 31.31. HRMS (ESI): m/z [M + Na]+ calcd for C33H33FNaO5: 551.2204; found: 551.2194. 4-Chloro-Phenyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3n) Yield: 45.8 mg (75%); colorless syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.41–7.19 (m, 17 H), 6.99 (t, J = 6.1 Hz, 2 H), 5.66 (d, J = 3.0 Hz, 1 H), 4.97 (d, J = 11.5 Hz, 1 H), 4.70–4.62 (m, 3 H), 4.41 (d, J = 11.6 Hz, 1 H), 4.36 (d, J = 11.6 Hz, 1 H), 4.10 (ddd, J = 11.9, 4.3, 2.3 Hz, 1 H), 4.03–3.97 (m, 2 H), 3.63 (dd, J = 9.3, 7.2 Hz, 1 H), 3.52 (dd, J = 9.4, 5.8 Hz, 1 H), 2.40 (td, J = 12.5, 3.6 Hz, 1 H), 2.20 (dd, J = 12.8, 4.5 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 155.51, 138.81, 138.45, 138.01, 129.40, 128.56, 128.44, 128.36, 128.31, 127.81, 127.78, 127.74, 127.69, 127.44, 126.94, 118.05, 96.86, 74.53, 74.50, 73.44, 72.86, 70.87, 70.67, 69.29, 31.20, 29.79. HRMS (ESI): m/z[M + Na]+ calcd for C33H33ClNaO5: 567.1909; found: 567.1895. 2-Methyl-Phenyl-3,4,6-tri-O-benzyl-2-deoxy-α-d-galactopyranoside (3p) Yield: 39.8 mg (76%); colorless syrup; α:β >30:1. 1H NMR (500 MHz, CDCl3): δ = 7.41–7.20 (m, 15 H), 7.15–7.08 (m, 3 H), 6.94–6.86 (m, 1 H), 5.71 (d, J = 1.9 Hz, 1 H), 4.99 (d, J = 11.5 Hz, 1 H), 4.73–4.62 (m, 3 H), 4.42 (d, J = 11.6 Hz, 1 H), 4.36 (d, J = 11.6 Hz, 1 H), 4.18–4.11 (m, 1 H), 4.03 (d, J = 7.6 Hz, 2 H), 3.67 (t, J = 8.4 Hz, 1 H), 3.53 (dd, J = 9.2, 5.5 Hz, 1 H), 2.42 (td, J = 12.5, 3.4 Hz, 1 H), 2.22–2.18 (m, 1 H), 2.17 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 154.98, 138.92, 138.37, 138.05, 130.69, 128.53, 128.41, 128.33, 128.30, 127.89, 127.74, 127.73, 127.62, 127.15, 126.95, 121.58, 114.24, 96.28, 74.51, 74.28, 73.47, 72.96, 70.78, 70.53, 69.18, 31.50, 16.3. HRMS (ESI): m/z [M + Na]+ calcd for C34H36NaO5: 547.2455; found: 547.2441.