Carbon Dioxide → HCID 66860324, compound

HRID 243750Notes

Reaction equation

HRID 243750 reaction equation
[C:1]([NH:4][C@@H:5]1[C@@H:18]([O:19][CH2:20][CH:21]=[CH2:22])[C@H:17]([OH:23])[C@@H:16]([CH2:24][OH:25])[O:15][C@@H:6]1[O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)(=[O:3])[CH3:2].[CH2:26](Br)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.[H-].[Na+].C(=O)=O>CN(C)C=O.O>[C:1]([NH:4][C@@H:5]1[C@@H:18]([O:19][CH2:20][CH:21]=[CH2:22])[C@H:17]([O:23][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@@H:16]([CH2:24][O:25][CH2:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[O:15][C@@H:6]1[O:7][CH2:8][C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1)(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 280Carbon DioxideHCID 7498Benzyl BromideHCID 24758Sodium hydride2×HCID 14886118Phenylmethyl 2-(acetylamino)-2-deoxy-3-O-2-propen-1-yl-α-D-glucopyranoside

Product 1

HCID 66860324HCID 66860324, compoundYield 178.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Procedure

A solution of benzyl 2-acetamido-3-O-allyl-2-deoxy-α-D-glucopyranoside 4 (ref.25; 10.5 g, 29.9 mmol) and benzyl bromide (7.7 ml, 65 mmol) in dry N,N-dimethylformamide (75 ml) was gradually added to a stirred suspension of sodium hydride (60% in mineral oil; 2.8 g, 70 mmol) in N,N-dimethylformamide (25 ml) under argon at 0° C. during 30 min, and the whole was stirred at room temperature for 24 h. A solid carbon dioxide was added and the excess of sodium hydride was decomposed with water and the mixture was evaporated. The solid residue was partitioned between toluene (500 ml) and water (100 ml), organic layer was washed with water (2×100 ml), dried (MgSO4) and evaporated. Chromatography of the residue on a silica gel column (500 g) in toluene-ethyl acetate (2:1) afforded 14.2 g (89%) of 5 as white solid, which was crystallized from toluene-n-heptane; m.p. 152-153° C., [α]D+109° (c 0.5, chloroform); ref.39: m.p. 137.5-138.5° C. (diethyl ether), [α]D+102° (c 1.0, chloroform). IR and 1H NMR spectra correspond with the respective data for the authentic sample described in ref.39. 1H NMR: 7.16-7.37 m, 15H (H-arom.); 5.87 ddt, 1 H, J=5.8, 5.8, 10.3, 17.1 (OCH2—CH═CH2); 5.56 bd, 1 H, J=9.6 (NHCOCH3); 5.23 dq, 1 H, J=1.7, 1.7, 1.7, 17.1 (OCH2—CH═CHH); 5.17 dq, 1 H, J=1.5, 1.5, 1.5, 10.3 (OCH2—CH═CHH); 4.90 d, 1 H, J=3.8 (H-1); 4.79 d, 1 H, J=10.6 (CH2-Ph); 4.70 d, 1 H, J=11.7 (CH2-Ph); 4.63 d, 1 H, J=12.2 (CH2-Ph); 4.53 d, 1 H, J=12.2 (CH2-Ph); 4.50 d, 1 H, J=10.6 (CH2-Ph); 4.45 d, 1 H, J=11.7 (CH2-Ph); 4.30 ddt, 1 H, J=1.4, 1.4, 5.2, 12.6 (OCHHCH═CH2); 4.29 ddd, 1 H, J=3.8, 9.6, 10.6 (H-2); 4.09 ddt, 1 H, J=1.4, 1.4, 6.1, 12.6 (OCHHCH═CH2); 3.81 ddd, 1 H, J=2.0, 4.1, 9.9 (H-5); 3.73 dd, 1 H, J=4.1, 10.6 (H-6a); 3.69 dd, 1 H, J=8.8, 9.9 (H-4); 3.64 dd, 1 H, J=2.0, 10.6 (H-6b); 3.59 dd, 1 H, J=8.8, 10.6 (H-3); 1.96 s, 3 H (NHCOCH3). 13C NMR: 169.7 (NHCOCH3), 138.0 (2C), 137.2 (C-arom.), 135.0 (OCH2—CH═CH2), 128.6 (2C), 128.4 (3C), 128.2 (2C), 128.1 (2C), 128.0 (2C), 127.8, 127.8 (2C), 127.6 (C-arom.), 116.9 (OCH2—CH═CH2), 97.3 (C-1), 80.8 (C-3), 78.0 (C-4), 75.0 (CH2-Ph), 73.7 (CH2-Ph), 73.4 (OCH2—CH═CH2), 71.2 (C-5), 69.6 (CH2-Ph), 68.5 (C-6), 52.5 (C-2), 23.4 (NHCOCH3). For C32H37NO6 calculated: relative molecular mass 531.6, monoisotopic mass 531.3. FAB MS, m/z: 532.2 [M+H]+. For C32H37NO6 (531.6) calculated: 72.29% C, 7.01% H, 2.63% N; found 72.44% C, 6.98% H, 2.68% N.

Workup

  1. customthe mixture was evaporated
  2. customThe solid residue was partitioned between toluene (500 ml) and water (100 ml), organic layer
  3. washwas washed with water (2×100 ml)
  4. dry with materialdried (MgSO4)
  5. customevaporated

Sources & evidence

ORD record
ord-802d00d0b2444492b0ee2c2f8cc6dc00
Source dataset
uspto-grants-2014_02
Patent number
US08653049B2

Reaction notes

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