Trifluoroacetic acid → 6-[(2,5-dioxopyrrolidin-1-yl)oxy]-N-(2-{[alpha-D-mannopyranosyl-(1->3)-[alpha-D-mannopyranosyl-(1->6)]-alpha-D-mannopyranosyl]oxy}ethyl)-6-oxohexanamide

HRID 1488240Notes

Reaction equation

HRID 1488240 reaction equation
[C@H:1]1([O:12][C@H:13]2[C@H:18]([OH:19])[C@@H:17]([CH2:20][O:21][C@H:22]3[O:30][C@H:29]([CH2:31][OH:32])[C@@H:27]([OH:28])[C@H:25]([OH:26])[C@@H:23]3[OH:24])[O:16][C@H:15]([O:33][CH2:34][CH2:35][NH:36][C:37](=[O:45])[CH2:38][CH2:39][CH2:40][CH2:41][C:42]([OH:44])=[O:43])[C@H:14]2[OH:46])[O:9][C@H:8]([CH2:10][OH:11])[C@@H:6]([OH:7])[C@H:4]([OH:5])[C@@H:2]1[OH:3].[B-](F)(F)(F)F.CN(C(O[N:60]1[C:65](=[O:66])[CH2:64][CH2:63][C:61]1=[O:62])=[N+](C)C)C.CCN(C(C)C)C(C)C.C(O)(C(F)(F)F)=O>CN(C=O)C>[O:62]=[C:61]1[CH2:63][CH2:64][C:65](=[O:66])[N:60]1[O:43][C:42](=[O:44])[CH2:41][CH2:40][CH2:39][CH2:38][C:37]([NH:36][CH2:35][CH2:34][O:33][C@H:15]1[O:16][C@H:17]([CH2:20][O:21][C@H:22]2[O:30][C@H:29]([CH2:31][OH:32])[C@@H:27]([OH:28])[C@H:25]([OH:26])[C@@H:23]2[OH:24])[C@@H:18]([OH:19])[C@H:13]([O:12][C@H:1]2[O:9][C@H:8]([CH2:10][OH:11])[C@@H:6]([OH:7])[C@H:4]([OH:5])[C@@H:2]2[OH:3])[C@@H:14]1[OH:46])=[O:45]

Participants

6

Reactant 4

HCID 6422Trifluoroacetic acidHCID 81531DiisopropylethylamineHCID 98575222-(2,5-Dioxopyrrolidin-1-yl)-1,1,3,3-tetramethylisouronium tetrafluoroborateHCID 1317368536-({2-[(alpha-D-mannopyranosyl-(1->3)-[alpha-D-mannopyranosyl-(1->6)]-alpha-D-mannopyranosyl)oxy]ethyl}amino)-6-oxohexanoic acid

Product 1

HCID 1180022426-[(2,5-dioxopyrrolidin-1-yl)oxy]-N-(2-{[alpha-D-mannopyranosyl-(1->3)-[alpha-D-mannopyranosyl-(1->6)]-alpha-D-mannopyranosyl]oxy}ethyl)-6-oxohexanamide

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 6-({2-[(α-D-mannopyranosyl-(1→3)-[α-D-mannopyranosyl-(1→6)]-α-D-mannopyranosyl)oxy]ethyl}amino)-6-oxohexanoic acid (1.55 g, 2.294 mmol) in DMF (22 mL) at 0° C. was added TSTU (760 mg, 2.52 mmol) and DIPEA (0.52 mL, 2.98 mmol). After stirring at 0° C. for 1 hr, the reaction was quenched by the addition of TFA (371 μL, 4.82 mmol) and the resulting mixture was concentrated down to about 3 mL. The residue was transferred dropwise, via autopipette, to a tube containing anhydrous acetonitrile (45 mL). The white precipitate was collected through centrifugation (3000 rpm, 15 min, at 4° C.), washed with anhydrous AcCN (1 mL) and dried to yield the title compound. UPLC Method B: calculated for C30H48N2O21 772.27, observed m/e: 773.23 [M+1]; Rt=3.65 min. 1H NMR (D2O) δ 5.07-5.06 (1H, m), 4.84-4.83 (1H, m), 4.79-4.78 (1H, m), 4.06-4.01 (2H, m), 3.96-3.93 (2H, m), 3.87-3.83 (5H, m), 3.80-3.78 (1H, m), 3.75-3.69 (5H, m), 3.67-3.61 (4H, m), 3.57-3.52 (1H, m), 3.41-3.38 (2H, m), 2.91 (4H, s), 2.75-2.71 (2H, m), 2.29-2.25 (2H, m), 1.75-1.58 (4H, m).

Workup

  1. concentrationthe resulting mixture was concentrated down to about 3 mL
  2. customThe residue was transferred dropwise, via autopipette, to a tube
  3. additioncontaining anhydrous acetonitrile (45 mL)
  4. customThe white precipitate was collected through centrifugation (3000 rpm, 15 min, at 4° C.)
  5. washwashed with anhydrous AcCN (1 mL)
  6. customdried

Sources & evidence

ORD record
ord-7f7871dbee72481d9e90e8666c6839d3
Source dataset
uspto-grants-2016_08
Patent number
US09427475B2

Reaction notes

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