Pyridine → diethyl (((2 S,4R,5 S,6R)-3-(acetoxyimino)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)methyl)phosphonate

HRID 522187Notes

Reaction equation

HRID 522187 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:13]([CH2:23][O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:12][C@H:11]([CH2:32][P:33](=[O:40])([O:37][CH2:38][CH3:39])[O:34][CH2:35][CH3:36])[C:10]1=[N:41][OH:42])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C=CC=CC=1.[CH3:49][C:50](OC(C)=O)=[O:51]>C(Cl)Cl.CN(C1C=CN=CC=1)C>[C:50]([O:42][N:41]=[C:10]1[C@@H:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[C@H:14]([O:15][CH2:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C@@H:13]([CH2:23][O:24][CH2:25][C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[O:12][C@@H:11]1[CH2:32][P:33](=[O:40])([O:34][CH2:35][CH3:36])[O:37][CH2:38][CH3:39])(=[O:51])[CH3:49]

Participants

6

Reactant 3

HCID 1049PyridineHCID 7918Acetic AnhydrideHCID 131735509diethyl (((2S,4R,5S,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-3-(hydroxyimino)tetrahydro-2H-pyran-2-yl)methyl)phosphonate

Product 1

HCID 131735511diethyl (((2 S,4R,5 S,6R)-3-(acetoxyimino)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)methyl)phosphonateYield 70%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of diethyl (((2S,4R,5S,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-3-(hydroxyimino)tetrahydro-2H-pyran-2-yl)methyl)phosphonate (2.0 g, 3.35 mmol, 1.0 equiv) in dry DCM (40 mL) was added catalytic DMAP, pyridine (2.1 mL, 26.8 mmol, 8.0 equiv) and Ac2O (1.26 mL, 13.4 mmol, 4.0 equiv) slowly. The mixture was stirred at room temperature for 16 hours and then the concentrated in vacuo. The product thus obtained was then purified by silica gel chromatography, eluting with MeOH:acetone:chloroform:petroleum ether (0.5:0.5:1:8), to give diethyl (((2 S,4R,5 S,6R)-3-(acetoxyimino)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)methyl)phosphonate as a colorless oil (1.5 g, 70%). 1H NMR (400 MHz, CDCl3) δ 7.32 (dddd, J=21.0, 10.3, 8.1, 6.0 Hz, 13H), 7.20 (ddq, J=8.2, 5.4, 3.0 Hz, 2H), 5.48-5.38 (m, 1H), 4.90 (d, J=11.6 Hz, 1H), 4.72 (d, J=11.5 Hz, 1H), 4.62-4.44 (m, 5H), 4.18-4.02 (m, 4H), 3.95-3.83 (m, 2H), 3.63 (qd, J=10.1, 4.8 Hz, 2H), 2.61-2.46 (m, 1H), 2.26-2.15 (m, 4H), 1.32 (td, J=7.1, 1.9 Hz, 6H). MS ESI (M+1) 639.8; calc for C34H42NO9P 639.3.

Workup

  1. concentrationthe concentrated in vacuo
  2. customThe product thus obtained
  3. customwas then purified by silica gel chromatography
  4. washeluting with MeOH:acetone:chloroform:petroleum ether (0.5:0.5:1:8)

Sources & evidence

ORD record
ord-f477823523024c3ea9cdd23314cf30c6
Source dataset
uspto-grants-2016_05
Patent number
US09328134B2

Reaction notes

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