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DOI: 10.1055/a-2186-1485
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Japan/Netherlands Gratama Workshop

Practical Site-Selective Oxidation of Glycosides with Palladium(II) Acetate/Neocuproine

Niels R. M. Reintjens
,
Imke M. A. Bartels
,
Nittert Marinus
,
Sarina C. Massmann
,
Daan V. Bunt
,
Marthe T. C. Walvoort
,
Martin D. Witte  ∗
,
Adriaan J. Minnaard  ∗
I.M.A.B. and S.C.M. thank ARC-CBBC for funding. N.M. thanks NWO (project number 718.016.001) for funding.
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Abstract

The palladium-catalyzed oxidation of the secondary C(3) hydroxy group of glycopyranosides has set a mark in the selective modification of unprotected carbohydrates. The preformed catalyst [(neocuproine)PdOAc]2(OTf)2 oxidizes di- and oligosaccharides, as well as monosaccharides. Here, we provide a more convenient protocol for this reaction in which the Pd catalyst is formed in situ from Pd(OAc)2 and neocuproine in methanol at 50 °C. Together with a simplified product isolation, this protocol was applied to a series of mono- and disaccharides, and has been applied on a 10 gram scale. The protocol is also valuable as a screening method to determine whether more-extensive studies using the preformed catalyst are worthwhile.

Keywords

glycosides - oxidation - palladium catalysis - neocuproine - site-selectivity - regioselectivity

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2186-1485.
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Publication History

Received: 12 September 2023

Accepted after revision: 04 October 2023

Accepted Manuscript online:
04 October 2023

Article published online:
09 November 2023

© 2023. This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)

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  • 44 Compounds 6–16; General ProcedureBQ (114 mg, 1.05 mmol, 1.05 equiv), neocuproine (10.5 mg, 50 μmol, 5 mol%), and Pd(OAc)2 (11.2 mg, 50 μmol, 5 mol%) were added to a solution of the appropriate substrate (1.0 mmol, 1 equiv) in MeOH (0.2 M). The reactions were monitored by 1H NMR analysis of a 50 μL portion of the reaction mixture diluted with CD3OD. After stirring overnight, the mixture was concentrated in vacuo and the residue was dissolved in H2O (15 mL; Milli-Q), and the solution was washed with Et2O (2 × 30 mL). The aqueous layer was filtered twice through a 1.0 μm pore-size syringe filter and once through a 0.45 μm pore-size syringe filter, then concentrated in vacuo.
  • 45 Characterization data for 8: amorphous solid; yield: 0.14 g, 0.69 mmol (77%). 1H NMR (400 MHz, CD3OD): d = 5.39 (d, J = 4.2 Hz, 1 H), 4.20–4.14 (m, 1 H), 3.95 (dt, J = 12.4, 6.2 Hz, 1 H), 3.89–3.77 (m, 3 H), 2.88 (ddd, J = 13.9, 4.6, 1.1 Hz, 1 H), 2.43 (dd, J = 13.9, 0.9 Hz, 1 H), 1.15 (dd, J = 12.2, 6.2 Hz, 6 H). 13C NMR (101 MHz, CD3OD): d = 207.6, 97.9, 76.6, 74.2, 70.0, 62.6, 47.1, 23.5, 21.4. HRMS(ESI–): m/z [M–H]– calcd for C9H15O5: 203.0925; found: 203.0925.
  • 46 Characterization data for 11: amorphous solid; yield: 0.15 g, 0.85 mmol (85%) [+ 20 mg (0.11 mmol) starting material]. 1H NMR (400 MHz, CD3OD): δ = 4.99 (d, J = 4.4 Hz, 1 H), 4.42 (dd, J = 4.4, 1.5 Hz, 1 H), 3.89 (dd, J = 9.4, 1.4 Hz, 1 H), 3.76–3.68 (m, 1 H), 3.38 (s, 4 H), 1.39 (d, J = 6.2 Hz, 3 H). 13C NMR (101 MHz, CD3OD): δ = 206.5, 103.6, 78.8, 76.1, 72.0, 55.7, 18.9. HRMS(ESI–): m/z [M–H]– calcd for C7H11O5: 175.0612; found: 175.0612.
  • 47 Characterization data for 12: amorphous solid; yield: 0.15 g 0.74 mmol (85%) [+ starting material: 15 mg (7 μmol)]. 1H NMR (400 MHz, CD3OD): δ = 5.11 (d, J = 4.2 Hz, 1 H), 4.49 (dd, J = 4.1, 1.2 Hz, 1 H), 4.45 (d, J = 9.8 Hz, 1 H), 4.08 (d, J = 9.8 Hz, 1 H), 3.44 (d, J = 4.8 Hz, 3 H). 13C NMR (101 MHz, CD3OD) δ = 205.4, 104.3, 76.0, 75.0, 75.0, 56.2. HRMS (ESI–): m/z [M–H]– calcd for C7H9O7: 205.0354; found: 205.0354.
  • 48 Characterization data for 13: amorphous solid; yield: 0.22 g, 0.73 mmol (73%). 1H NMR (400 MHz, CD3OD): δ = 5.08 (d, J = 4.3 Hz, 1 H), 4.41 (dd, J = 4.2, 1.2 Hz, 1 H), 4.27 (dd, J = 9.7, 1.2 Hz, 1 H), 4.06–3.92 (m, 2 H), 3.68 (ddd, J = 9.7, 4.4, 2.0 Hz, 1 H), 3.43 (s, 3 H), 0.98 (s, 9 H), 0.16 (s, 6 H). 13C NMR (101 MHz, CD3OD): δ = 207.0, 103.7, 76.8, 76.0, 73.2, 63.9, 55.6, 26.4, –5.1, –5.2. HRMS (ESI): m/z [M + Na]+ calcd for C13H26NaO6Si: 329.1391; found: 329.1391.
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  • 52 Characterization data for 16: colorless oil; yield: 0.25 g, 0.62 mmol (62%). 1H NMR (400 MHz, CD3OD): δ = 7.42–7.35 (m, 3 H), 7.09 (d, J = 8.6 Hz, 2 H), 6.79 (d, J = 8.6 Hz, 2 H), 4.39 (d, J = 10.0 Hz, 1 H), 4.23 (s, 2 H), 4.11–3.90 (m, 5 H), 3.82 (dd, J = 12.1, 4.7 Hz, 1 H), 3.49 (ddd, J = 10.0, 4.8, 1.9 Hz, 1 H), 1.35 (t, J = 7.0 Hz, 4 H). 13C NMR (101 MHz, CD3OD): δ = 208.4, 158.9, 140.1, 139.3, 135.0, 132.8, 131.7, 130.8, 130.3, 128.0, 115.4, 85.2, 84.7, 78.6, 74.0, 64.4, 62.9, 39.2, 15.2. HRMS(ESI–): m/z [M–H]– calcd for C21H22ClO6: 405.1110 and 407.1081; found: 405.1105 and 407.1076.
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  • 54 Characterization data for 20: isolated as an oil, together with 21; yield: 51 mg, 0.11 mmol (48%). 1H NMR (400 MHz, CD3OD): δ = 8.13 (s, 1 H), 8.03–7.96 (m, 1 H), 7.41–7.31 (m, 2 H), 6.91–6.82 (m, 3 H), 5.80 (s, 1 H), 4.79 (d, J = 9.3 Hz, 1 H), 4.09–3.92 (m, 2 H), 3.91–3.85 (m, 1 H), 3.20 (s, 3 H). 13C NMR (101 MHz, CD3OD): δ = 177.8, 173.5, 162.9, 158.7, 156.2, 154.2, 131.3, 127.9, 125.8, 124.0, 117.9, 117.5, 116.2, 110.1, 87.6, 86.1, 83.3, 74.1, 59.6, 52.6. HRMS (ESI): m/z [M–H]– calcd for C22H21O10 [M+H]+: 445.1129; found: 445.1124.
  • 55 Characterization data for 23: isolated as an oil together with 24; yield: 96 mg, 0.32 mmol (32%). 1H NMR (400 MHz, CD3OD): δ = 8.44 (d, J = 2.7 Hz, 1 H), 8.10 (dd, J = 9.0, 2.8 Hz, 1 H), 6.94 (d, J = 9.0 Hz, 1 H), 4.82 (d, J = 10.0 Hz, 1 H), 4.54 (dd, J = 10.0, 1.6 Hz, 1 H), 4.44 (dd, J = 10.0, 1.5 Hz, 1 H), 3.95 (dd, J = 12.3, 1.9 Hz, 1 H), 3.84 (dd, J = 12.3, 4.8 Hz, 1 H), 3.55 (ddd, J = 10.0, 4.8, 2.0 Hz, 1 H). 13C NMR (101 MHz, CD3OD): δ = 208.4, 163.0, 141.9, 127.3, 126.4, 126.0, 116.6, 84.8, 78.8, 78.1, 74.0, 62.9. HRMS (ESI–): m/z [M–H]– calcd for C12H12NO8: 298.0568; found: 298.0563.
  • 56 Characterization data for 24: isolated as an oil together with 23; yield: 26 mg, 90 μmol (9%). 1H NMR (400 MHz, CD3OD): δ = 8.22 (d, J = 2.8 Hz, 1 H), 8.08 (dd, J = 8.9, 2.8 Hz, 1 H), 6.88 (d, J = 9.1 Hz, 1 H), 5.37 (s, 1 H), 4.43 (d, J = 9.3 Hz, 1 H), 4.02 (d, J = 10.3 Hz, 1 H), 3.94–3.79 (m, 2 H), 3.68 (t, J = 9.4 Hz, 1 H). 13C NMR (101 MHz, CD3OD): δ = 202.1, 162.0, 141.8, 126.2, 125.2, 124.6, 115.5, 82.7, 81.3, 78.6, 76.2, 62.7. HRMS (ESI–): m/z [M–H]– calcd for C12H12NO8: 298.0568; found: 298.0564.