Ammonium Chloride → HCID 68909415, compound

HRID 1427329Notes

Reaction equation

HRID 1427329 reaction equation
[Br:1][C@H:2]1[C@H:8]2[C@H:5]([C:6](=[O:9])[O:7]2)[CH2:4][C@H:3]1[NH:10][C:11]([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[BH4-].[Li+].CCOC(C)=O.CCCCCC.[NH4+].[Cl-]>C(OCC)C>[Br:1][C@@H:2]1[C@H:3]([NH:10][C:11]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)([C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[CH2:4][C@@H:5]([CH2:6][OH:9])[C@H:8]1[OH:7]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 4148881Lithium borohydrideHCID 21226206Ethyl acetate hexaneHCID 86627067HCID 86627067, compound

Product 1

HCID 68909415HCID 68909415, compoundYield 100.8%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

(1R,3R,4R,5R)-4-bromo-3-(tritylamino)-6-oxabicyclo[3.2.0]heptan-7-one (0.6 g, 0.0013382 mol) was dissolved in diethyl ether (20 mL) and the mixture was cooled to 0° C. Lithium tetrahydroborate (0.087 g, 0.004015 mol) was added in one portion and the mixture was stirred at 0° C. for 1 hour, then allowed to warm to ambient temperature and stirred for a further 1 hour. TLC (20% EtOAc/Hexane) showed no starting material. The reaction mixture was cooled to 0° C. at which point saturated NH4Cl aq (20 mL) was added dropwise maintaining a temperature less than 5° C. The mixture was allowed to warm to ambient temperature and extracted with methylene chloride (3×20 mL). The organics were combined and dried over Na2SO4, filtered and concentrated to afford the title compound (0.61 g) as a white solid which was used without further purification. 1H NMR (300 MHz, CD3OD, δ): 7.56 (m, 6H), 7.25 (m, 9H), 4.15 (m, 1H), 3.55 (m, 1H), 3.40 (m, 2H), 2.90 (m, 1H), 2.53 (m, 1H) and 1.63 (m, 2H). LCMS: Rf=13.30 mins, ES+Na=474 (AA).

Workup

  1. temperatureto warm to ambient temperature
  2. stirringstirred for a further 1 hour
  3. additionwas added dropwise
  4. temperaturemaintaining a temperature less than 5° C
  5. temperatureto warm to ambient temperature
  6. extractionextracted with methylene chloride (3×20 mL)
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-d9e7bb8351344f3ea52ec2243a5749fa
Source dataset
uspto-grants-2015_01
Patent number
US08933225B2

Reaction notes

Loading…