Ammonium Chloride → HCID 86748311, compound

HRID 1492014Notes

Reaction equation

HRID 1492014 reaction equation
[Br-].[C:2]([CH2:6][CH2:7][CH2:8][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:4][CH3:5])=[O:3].CC(C)([O-])C.[K+].[Si:34]([O:41][C@@H:42]1[CH2:46][O:45][C@H:44]([C:47]2[CH:48]=[N:49][CH:50]=[CH:51][CH:52]=2)[C@@H:43]1[CH2:53][CH2:54][CH:55]=O)([C:37]([CH3:40])([CH3:39])[CH3:38])([CH3:36])[CH3:35].[Cl-].[NH4+]>O1CCCC1.CCOCC>[Si:34]([O:41][C@@H:42]1[CH2:46][O:45][C@H:44]([C:47]2[CH:48]=[N:49][CH:50]=[CH:51][CH:52]=2)[C@@H:43]1[CH2:53][CH2:54]/[CH:55]=[CH:8]\[CH2:7][CH2:6][C:2]([O:4][CH3:5])=[O:3])([C:37]([CH3:40])([CH3:39])[CH3:38])([CH3:36])[CH3:35]

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 11015714(4-Methoxy-4-oxobutyl)triphenylphosphonium bromideHCID 18657617HCID 18657617, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 86748311HCID 86748311, compoundYield 69.7%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

To a suspension of 61.85 g (0.137 mol) of (3-carbomethoxy-1-propyl)triphenylphosphoniumbromide in 290 ml of tetrahydrofurane are added dropwise at 0° C. over argon with stirring, 116 ml (0.116 mol) of 1M solution of potassium tert-butoxide in tetrahydrofurane over a period of 20 min. The mixture is stirred at 0° C. for 1 h and a solution of 29.6 g of (2S,3S,4S)-3-[4-(t-butyldimethylsilyloxy)-2-(3-pyridyl)tetrahydrofuran-3-yl]propanal in 150 ml of tetrahydrofurane is added dropwise over a period of 15 min. The mixture is stirred at room temperature for an additional one h, 50 ml of concentrated aqueous ammonium chloride is added and the mixture is diluted with 2000 ml of ether. The mixture is washed with water and brine and the organic layer is dried (MgSO4) and evaporated. The residue is triturated with ether, the mixture is allowed to stand in the refrigerator overnight and the precipitated triphenylphosphine oxide is filtered and washed with ether. The combined filtrates are evaporated to dryness and the residue is subjected to flash chromatography on silica gel (5×30 cm2) using methylene chloride-ethyl acetate (1:1) as eluent to give 25.8 g of methyl (Z)-(2S,3S,4S)-7-[4-(t-butyldimethylsilyloxy)-2-(3-pyridyl)-tetrahydrofuran-3-yl]-4-heptenoate as an oil with elemental analysis: C,65.55; H,8.95; N,3.18 (theory: C,65.83; H,8.88; N,3.33) and optical rotation [α]D 25=+9.27 (methanol).

Workup

  1. additionare added dropwise at 0° C. over argon
  2. stirringThe mixture is stirred at 0° C. for 1 h
  3. additionis added
  4. washThe mixture is washed with water and brine
  5. dry with materialthe organic layer is dried (MgSO4)
  6. customevaporated
  7. customThe residue is triturated with ether
  8. customto stand in the refrigerator overnight
  9. filtrationthe precipitated triphenylphosphine oxide is filtered
  10. washwashed with ether
  11. customThe combined filtrates are evaporated to dryness

Sources & evidence

ORD record
ord-22a95b6cc487455c92899a9eceb99019
Source dataset
uspto-grants-1994_12
Patent number
US05371096

Reaction notes

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