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Synlett 2014; 25(09): 1325-1330
DOI: 10.1055/s-0033-1341232
letter
© Georg Thieme Verlag Stuttgart · New York

Copper(II) Triflate as a Mild and Efficient Catalyst for Ferrier Glycosylation: Synthesis of 2,3-Unsaturated O-Glycosides

Batthula Srinivas
D-207, Discovery Laboratory, Organic and Biomolecular Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad-500 007, India   Fax: +91(40)27160387   Email: skashyap@iict.res.in
,
Thurpu Raghavender Reddy
D-207, Discovery Laboratory, Organic and Biomolecular Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad-500 007, India   Fax: +91(40)27160387   Email: skashyap@iict.res.in
,
Palakodety Radha Krishna*
D-207, Discovery Laboratory, Organic and Biomolecular Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad-500 007, India   Fax: +91(40)27160387   Email: skashyap@iict.res.in
,
Sudhir Kashyap*
D-207, Discovery Laboratory, Organic and Biomolecular Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad-500 007, India   Fax: +91(40)27160387   Email: skashyap@iict.res.in
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Further Information

Publication History

Received: 20 February 2014

Accepted after revision: 24 March 2014

Publication Date:
10 April 2014 (online)

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Abstract

Various acceptors including carbohydrates, amino acids, natural products, and hydroxylamine derivatives were coupled with 3,4,6-tri-O-acetyl-d-glucal in the presence of Cu(OTf)2 as catalyst. The protocol offers facile and efficient Ferrier glycosylation for the synthesis of 2,3-unsaturaed O-glycosides in good yields and high anomeric selectivity.

Key words

glycosides - glycosylation - glycoconjugates - Ferrier reaction - Lewis acid

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett. Included are general synthesis information, characterization data, and 1H and 13C NMR spectra of all the compounds.
  • Supporting Information
 

  • References and Notes

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  • 17 Cu(OTf)2 Mediated Ferrier Glycosylation; Typical Procedure: To a stirred solution of 3,4,6-tri-O-acetyl-d-glucal 1 (1 equiv) and acceptor (1.2 equiv) in anhydrous MeCN (2 mL/mmol) under an atmosphere of argon was added Cu(OTf)2 (2 mol%) at r.t. The reaction mixture was stirred until complete consumption of the starting material (glycal). The solvent was concentrated in vacuo, the crude residue was re-dissolved in dichloromethane and loaded on a silica gel column. The product was purified by silica gel chromatography (hexane–EtOAc) to afford the 2,3-unsaturated O-glycosides in excellent yields. The identities of all the Ferrier products were confirmed by IR, 1H NMR, 13C NMR and MS/HRMS spectroscopic analysis. p-Trifuoromethylphenyl 4,6-Di-O-acetyl-2,3-dideoxy-erythro-hex-2-eno-1-thio-α-d-pyranoside (3f): Yellow oil; [α]D +222.368 (c 19.0, CHCl3). IR (CHCl3): 3019, 2955, 2929, 1743, 1606, 1370, 1325, 1226, 1166, 1124, 1061, 1015, 952, 833, 772, 750, 667, 599 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.64 (d, J = 8.1 Hz, 2 H, Ar-H), 7.56 (d, J = 8.3 Hz, 2 H, Ar-H), 6.05 (dt, J = 11.3, 1.2 Hz, 1 H, H-3), 5.92 (dt, J = 10.1, 1.5 Hz, 1 H, H-2), 5.87 (br s, 1 H, H-1), 5.41 (dd, J = 9.4, 1.9 Hz, 1 H, H-4), 4.42 (m, 1 H, H-5), 4.29 (d, J = 12.1, 5.6 Hz, 1 H, Ha-6), 4.24 (dd, J = 12.1, 2.6 Hz, 1 H, Hb-6), 2.12 (s, 3 H), 2.04 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 170.6, 170.2, 130.2, 128.3, 127.8, 125.7, 125.6, 82.7, 67.6, 64.9, 62.8, 20.9, 20.6. MS (ESI): m/z (%) = 408 (100) [M + NH4]+. Cycloproylmethyl 4,6-Di-O-acetyl-2,3-dideoxy-α-d-erythro-hex-2-enopyranoside (3g): Colorless oil. IR (CHCl3): 3017, 2920, 2852, 1741, 1370, 1219, 1036, 972, 907, 751, 667 cm–1. 1H NMR (500 MHz, CDCl3): δ = 5.91–5.885 (m, 2 H, H-3, H-2), 5.31 (dd, J = 9.5, 1.4 Hz, 1 H, H-4), 5.08 (br s, 1 H, H-1), 4.23 (dd, J = 11.9, 5.3 Hz, 1 H, Ha-6), 4.18 (dd, J = 11.8, 2.4 Hz, 1 H, Hb-6), 4.15 (m, H-5), 3.51 (dd, J = 10.4, 7.3 Hz, 1 H, OHCH), 3.43 (dd, J = 10.4, 6.9 Hz, 1 H, OHCH), 2.09 (s, 3 H, OAc), 2.09 (s, 3 H, OAc), 1.15–1.09 (m, 1 H, cyclopropyl), 0.59–0.55 (m, 2 H, cyclopropyl), 0.28–0.20 (m, 2 H, cyclopropyl). 13C NMR (75 MHz, CDCl3): δ = 170.6, 170.2, 128.9, 127.8, 93.8, 73.4, 66.8, 65.2, 63.0, 20.9, 20.7, 10.5, 3.2, 3.0. MS (ESI): m/z (%) = 302 (100) [M + NH4]+. (2,5-Dioxopyrrolidine-1-yl)-oxy 4,6-Di-O-acetyl-2,3-dideoxy-α-d-erythro-hex-2-enopyranoside (3i): Colorless oil; [α]D +150.000 (c 10.4, CHCl3). IR (CHCl3): 2926, 2853, 1724, 1432, 1370, 1220, 1206, 1108, 1045, 907, 814, 771, 650, 606 cm–1. 1H NMR (500 MHz, CDCl3): δ = 6.15 (d, J = 10.2 Hz, 1 H, H-3), 6.01 (dt, J = 10.2, 2.1 Hz, 1 H, H-2), 5.57 (br s, 1 H, H-1), 5.45 (ddd, J = 10.1, 3.4, 1.7 Hz, 1 H, H-4), 4.60 (dt, J = 10.1, 2.8 Hz, 1 H, H-5), 4.32 (dd, J = 12.5, 3.4 Hz, 1 H, Ha-6), 4.18 (dd, J = 12.5, 2.3 Hz, 1 H, Hb-6), 2.74 (s, 4 H, COC2 H 4CO), 2.12 (s, 3 H, OAc), 2.10 (s, 3 H, OAc). 13C NMR (75 MHz, CDCl3): δ = 171.1, 170.7, 170.2, 133.5, 122.9, 98.1, 68.2, 64.2, 61.8, 25.5, 20.9, 20.7. MS (ESI): m/z (%) = 345 (100) [M + NH4]+. 9-Fluorenylmethyl 4,6-Di-O-acetyl-2,3-dideoxy-α-d-erythro-hex-2-enopyranoside (3k): Viscous liquid; [α]D +68.750 (c 0.8, CHCl3). IR (CHCl3): 2923, 1743, 1447, 1371, 1231, 1038, 741, 610 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.77 (d, J = 7.5 Hz, 2 H, Ar-H), 7.63 (m, 2 H, Ar-H), 7.40 (t, J = 7.5 Hz, 2 H, Ar-H), 7.31 (d, J = 7.5 Hz, 2 H, Ar-H), 5.94–5.93 (m, 2 H, H-3, H-2), 5.32 (d, J = 9.3 Hz, 1 H, H-4), 5.12 (br s, 1 H, H-1), 4.23–4.17 (m, 2 H, Ha-6, OHCH), 4.16–4.12 (m, 2 H, OHCH, H-5), 4.10 (dd, J = 9.3, 7.5 Hz, 1 H, Hb-6), 3.75 (dd, J = 9.3, 7.6 Hz, 1 H, OCH2CH), 2.12 (s, 3 H, -OAc), 1.93 (s, 3 H, -OAc). 13C NMR (75 MHz, CDCl3): δ = 170.6, 170.2, 144.6, 144.4, 141.0, 129.2, 127.6, 127.4, 126.8, 125.0, 119.8, 94.7, 71.2, 67.1, 65.2, 65.2, 62.8, 47.7, 20.9, 20.5. MS (ESI): m/z (%) = 431.10 (100) [M + Na]+. HRMS (ESI): m/z calcd for C24H28NO6 + [M + NH4]+ 426.19116; found 426.19118.