N-bromobutanimide → HCID 86701099, compound

HRID 1396238Notes

Reaction equation

HRID 1396238 reaction equation
[CH3:1][O:2][C:3]1[CH:42]=[CH:41][C:6]([CH2:7][O:8][C@@H:9]2[C@@H:17]([CH2:18][OH:19])[O:16][CH:15]3[CH:11]([N:12]=[C:13]([N:20]([CH2:28][CH2:29][CH3:30])[C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[S:14]3)[C@H:10]2[O:31][CH2:32][C:33]2[CH:38]=[CH:37][C:36]([O:39][CH3:40])=[CH:35][CH:34]=2)=[CH:5][CH:4]=1.C1C(=O)N(Br)C(=O)C1>CCCC[N+](CCCC)(CCCC)CCCC.[Br-].ClCCl.O.CC1(C)N([O])C(C)(C)CCC1>[CH:18]([C@H:17]1[O:16][C@H:15]2[C@H:11]([N:12]=[C:13]([N:20]([CH2:28][CH2:29][CH3:30])[C:21](=[O:27])[O:22][C:23]([CH3:24])([CH3:25])[CH3:26])[S:14]2)[C@@H:10]([O:31][CH2:32][C:33]2[CH:38]=[CH:37][C:36]([O:39][CH3:40])=[CH:35][CH:34]=2)[C@@H:9]1[O:8][CH2:7][C:6]1[CH:41]=[CH:42][C:3]([O:2][CH3:1])=[CH:4][CH:5]=1)=[O:19]

Participants

7

Reactant 2

HCID 67184N-bromobutanimideHCID 86701100HCID 86701100, compound

Product 1

HCID 86701099HCID 86701099, compoundYield 60.2%

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 2724126TempoCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a mixture of tert-butyl (5R,6S,7R)-6,7-bis(4-methoxybenzyloxy)-5-(hydroxymethyl)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazol-2-yl(propyl)carbamate (2 g, 3.32 mmol), KHCO3 (1.49 bg, 15 mmol), TBAB (53 mg, 0.16 mmol) and TEMPO (26 mg, 0.17 mmol) in dichloromethane (60 mL) and H2O (12 mL) was added NBS (592 mg, 3.33 mmol) at 15° C. After stirred for 30 min, the reaction mixture was quenched by saturated Na2SO3 (10 mL). The organic layer was dried over anhydrous magnesium sulfate and condensed to provide a residue, which was purified by silica gel column, eluted with 20-30% AcOEt in dichloromethane to give compound 20 as a yellow syrup (1.2 g, purity 60%). (ES, m/z): [M+H]+ 601.1. 1H NMR (300 MHz, CDCl3) δ 9.61 (s, 1H), 7.23-7.28 (m, 4H), 6.82-6.86 (m, 4H), 6.19-6.21 (d, J=6.9 Hz, 1H), 4.60-4.67 (m, 2H), 4.41-4.55 (m, 3H), 4.02-4.03 (m, 1H), 3.88-3.93 (m, 1H), 3.68-3.81 (m, 9H), 1.46-1.53 (m, 11H), 0.83-0.86 (t, J=7.5 Hz, 3H).

Workup

  1. customthe reaction mixture was quenched by saturated Na2SO3 (10 mL)
  2. dry with materialThe organic layer was dried over anhydrous magnesium sulfate and condensed
  3. customto provide a residue, which
  4. customwas purified by silica gel column
  5. washeluted with 20-30% AcOEt in dichloromethane

Sources & evidence

ORD record
ord-ac6ec23874dc40a6a49915c52fb99547
Source dataset
uspto-grants-2014_12
Patent number
US08901087B2

Reaction notes

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