m-Chloroperbenzoic acid → t-Butyldimethylsilyl 3-O-allyloxycarbonyl-2-azido-6-O-benzyl-2-deoxy-4-O-(1,5-dihydro-3-oxo-3lambda5-3H-2,4,3-benzodioxaphosphepin-3-yl)-beta-D-glucopyranoside

HRID 628190Notes

Reaction equation

HRID 628190 reaction equation
[CH2:1]([O:4][C:5]([O:7][C@H:8]1[C@H:21]([OH:22])[C@@H:20]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:19][C@@H:10]([O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])[C@@H:9]1[N:32]=[N+:33]=[N-:34])=[O:6])[CH:2]=[CH2:3].N1C=NN=N1.C(N(CC)[P:43]1[O:49][CH2:48][C:47]2[CH:50]=[CH:51][CH:52]=[CH:53][C:46]=2[CH2:45][O:44]1)C.C1C=C(Cl)C=C(C(OO)=[O:64])C=1>C(Cl)Cl>[CH2:1]([O:4][C:5]([O:7][C@H:8]1[C@H:21]([O:22][P:43]2(=[O:64])[O:44][CH2:45][C:46]3[CH:53]=[CH:52][CH:51]=[CH:50][C:47]=3[CH2:48][O:49]2)[C@@H:20]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:19][C@@H:10]([O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:13])[CH3:14])[C@@H:9]1[N:32]=[N+:33]=[N-:34])=[O:6])[CH:2]=[CH2:3]

Participants

6

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 41968792,4,3-Benzodioxaphosphepin-3-amine, N,N-diethyl-1,5-dihydro-HCID 16216114t-Butyldimethylsilyl 3-O-allyloxycarbonyl-2-azido-6-O-benzyl-2-deoxy-beta-D-glucopyranosideHCID 178418441HCID 178418441, compound

Product 1

HCID 16216115t-Butyldimethylsilyl 3-O-allyloxycarbonyl-2-azido-6-O-benzyl-2-deoxy-4-O-(1,5-dihydro-3-oxo-3lambda5-3H-2,4,3-benzodioxaphosphepin-3-yl)-beta-D-glucopyranosideYield 89%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of compound 9 (1.30 g, 2.50 mmol) and 1H-tetrazole (3% wt, 10.0 mmol) in DCM (30 mL) was added N,N-diethyl-1,5-dihydro-3H-2,4,3-benzodioxaphosphepin-3-amine (1.20 g, 1.05 mmol). After the reaction mixture was stirred at room temperature for 15 min, it was cooled (−20° C.), stirred for another 10 min and then mCPBA (3.40 g, 50-55% wt, 10.0 mmol) was added. The reaction mixture was stirred at −20° C. for 20 min, and then quenched by the addition of saturated aqueous NaHCO3 (40 mL) and diluted with DCM (30 mL). The organic phase was washed with saturated aqueous NaHCO3 (2×60 mL) and brine (2×40 mL), dried (MgSO4) and filtered. Next, the filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography (hexane/ethyl acetate, 5/1-3/1, v/v) to give 10 as a pale yellow oil (1.48 g, 89%). Rf=0.40 (hexane/ethyl acetate, 1/1, v/v). [α]25D=−10.3° (c=1.0, CHCl3). 1H NMR (300 MHz, CDCl3): δ 7.35-7.15 (m, 9H, aromatic), 5.98-5.85 (m, 1H, OCH2CH═CH2), 5.65 (d, 1H, J=1.2 Hz, J=17.4 Hz, OCH2CH═CH2), 5.50 (d, 1H, J=1.2 Hz, J=10.5 Hz, OCH2CH═CH2), 5.18-5.01 (m, 4H, C6H4(CH2O)P), 3.81 (dd, 1H, J2,3=10.5 Hz, J3,4=9.3 Hz, H-3), 4.64-4.52 (m, 6H, H-1, H-4, OCH2CH═CH2, CH2Ph), 3.82 (d, 1H, J6a,6b=9.0 Hz, H-6a), 3.72-3.61 (m, 2H, H-5, H-6b), 3.41 (dd, 1H, J1,2=7.4 Hz, J2,3=10.5 Hz, H-2), 0.92 (s, 9H, SiC(CH3)3), 0.16 (s, 3H, Si(CH3)), 0.15 (s, 3H, Si(CH3)). 13C NMR (75 MHz, CDCl3): δ 154.38 (C═O), 138.02-127.56 (aromatic), 131.33 (OCH2CH═CH2), 118.99 (OCH2CH═CH2), 97.13 (C-1), 76.77 (C-3), 74.27 (C-4), 74.08 (C-5), 73.50 (CH2Ph), 69.06 (OCH2CH═CH2), 68.74 (C-6), 68.55 (OC6H4(CH2O)P), 68.50 (OC6H4(CH2O)P), 65.97 (C-2), 25.53 (SiC(CH3)3), 17.92 (SiC(CH3)3), −4.35 (Si(CH3)2), −5.28 (Si(CH3)2). HR MS (m/z) calculated for C31H42N3O10PSi[M+Na]+, 698.2275. found, 698.2315.

Workup

  1. temperatureit was cooled (−20° C.)
  2. stirringstirred for another 10 min
  3. stirringThe reaction mixture was stirred at −20° C. for 20 min
  4. customquenched by the addition of saturated aqueous NaHCO3 (40 mL)
  5. additiondiluted with DCM (30 mL)
  6. washThe organic phase was washed with saturated aqueous NaHCO3 (2×60 mL) and brine (2×40 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationNext, the filtrate was concentrated in vacuo
  10. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate, 5/1-3/1

Sources & evidence

ORD record
ord-6b003081352545bbbc9c69c19a30e802
Source dataset
uspto-grants-2016_04
Patent number
US09309276B2

Reaction notes

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