N-bromobutanimide → HCID 86701110, compound

HRID 1396259Notes

Reaction equation

HRID 1396259 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:17]([CH2:18][OH:19])[O:16][C@H:15]2[C@H:11]([N:12]=[C:13]([N:20]([CH2:28][CH2:29][F:30])[C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[S:14]2)[C@H:10]1[O:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1C(=O)N(Br)C(=O)C1>CCCC[N+](CCCC)(CCCC)CCCC.[Br-].ClCCl.O.CC1(C)N([O])C(C)(C)CCC1>[CH2:1]([O:8][C@@H:9]1[C@@H:17]([CH:18]=[O:19])[O:16][C@H:15]2[C@H:11]([N:12]=[C:13]([N:20]([CH2:28][CH2:29][F:30])[C:21](=[O:27])[O:22][C:23]([CH3:25])([CH3:24])[CH3:26])[S:14]2)[C@H:10]1[O:31][CH2:32][C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 2

HCID 67184N-bromobutanimideHCID 86701111HCID 86701111, compound

Product 1

HCID 86701110HCID 86701110, compoundYield 67%

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 2724126TempoCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of tert-butyl (3aR,5R,6S,7R,7aR)-6,7-bis(benzyloxy)-5-(hydroxymethyl)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazol-2-yl(2-fluoroethyl)carbamate (600 mg, 1.10 mmol), KHCO3 (495 mg, 4.95 mmol), TBAB (18 mg, 0.06 mmol) and TEMPO (9 mg, 0.06 mmol) in dichloromethane (17 mL) and water (2 mL) was treated with NBS (215 mg, 1.21 mmol) for 15 min at 10-15° C. The reaction mixture was quenched by saturated aqueous Na2SO3 (5 mL), extracted with dichloromethane (3×15 mL), dried over magnesium sulfate, and concentrated under vacuum to give a residue, which was purified by a silica gel column, eluting with 20% ethyl acetate in petroleum ether to provide compound 72 as a yellow syrup (0.4 g, 67%). (ES, m/z) [M+H]+ 545.0; 1H NMR (300 MHz, CDCl3) δ 9.64 (s, 1H), 7.23-7.39 (m, 10H), 6.09-6.11 (d, J=6.3 Hz, 1H), 4.55-4.75 (m, 5H), 4.34-4.45 (m, 2H), 4.13-4.28 (m, 3H), 3.90-4.12 (m, 2H), 1.54 (s, 9H).

Workup

  1. customThe reaction mixture was quenched by saturated aqueous Na2SO3 (5 mL)
  2. extractionextracted with dichloromethane (3×15 mL)
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated under vacuum
  5. customto give a residue, which
  6. customwas purified by a silica gel column
  7. washeluting with 20% ethyl acetate in petroleum ether

Sources & evidence

ORD record
ord-21c6c4af7e8940caae4a5acec95dcdc8
Source dataset
uspto-grants-2014_12
Patent number
US08901087B2

Reaction notes

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