Ammonium Chloride → HCID 69607407, compound

HRID 357278Notes

Reaction equation

HRID 357278 reaction equation
[CH2:1]([O:8][C@@H:9]1[CH2:31][C@@H:30]2[C@:25]([CH3:39])([CH2:26][CH2:27][C@H:28]([O:32][CH:33]3[CH2:38][CH2:37][CH2:36][CH2:35][O:34]3)[CH2:29]2)[C@@H:24]2[C@@H:10]1[C@H:11]1[C@:21]([CH3:40])([CH2:22][CH2:23]2)[C@@H:14]([C@H:15]([CH3:20])[CH2:16][CH2:17][CH:18]=[O:19])[CH2:13][CH2:12]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:41]([Mg]Cl)([CH3:43])[CH3:42].[NH4+].[Cl-]>C1COCC1>[CH2:1]([O:8][C@@H:9]1[CH2:31][CH:30]2[C@:25]([CH3:39])([CH2:26][CH2:27][C@H:28]([O:32][CH:33]3[CH2:38][CH2:37][CH2:36][CH2:35][O:34]3)[CH2:29]2)[C@@H:24]2[C@@H:10]1[C@H:11]1[C@:21]([CH3:40])([CH2:22][CH2:23]2)[C@@H:14]([C@H:15]([CH3:20])[CH2:16][CH2:17][CH:18]([OH:19])[CH:41]([CH3:43])[CH3:42])[CH2:13][CH2:12]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 10257003HCID 10257003, compoundHCID 178418918HCID 178418918, compound

Product 1

HCID 69607407HCID 69607407, compoundYield 77.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of compound 2009 (0.374 g, 0.679 mmol) in anhydrous THF (10 ml) under argon was treated with isopropylmagnesium chloride (2 ml, 2M in THF, 5.43 mmol) at room temperature. The reaction was stirred until no starting material remained by TLC. Aqueous NH4Cl solution (10%, 15 ml) was added to quench the reaction and the THF was removed in vacuo. Distilled H2O (5 ml) was added and the solution extracted 3× with 15 ml CH2Cl2. The combined organic layers were washed with aqueous saturated NaCl solution (15 ml), dried over anhydrous MgSO4, filtered and the solvent removed in vacuo. Flash chromatography (SiO2, 12:1 hexanes:EtOAc) gave compound 2010 (0.3117 g, 77%) as a white foam. 1 H NMR (500 MHz, CDCl3) δ: 7.35-7.34 (m, 5 H, benzyl Ar-H), 4.71-4.69 (m, 1 H, THP ether methine H), 4.585 (d, J=11.9 Hz, 1H, benzyl-CH2), 4.31 (d, J 12.0 Hz, 1/2 H, benzyl-CH2), 4.295 (d, J=12.0 Hz, 1/2 H, benzyl-CH2), 3.94-3.91 (m, 1H, THP, OCH2), 3.62-3.58 (m, 1 H, THP OCH2), 3.50-3.48 (m, 1H, C-3 H), 3.45 (s, 1H, C-7 H), 3.32-3.31 (m, 1H, C-24 H), 0.81 (s, 3 H, C-19 H), 0.63 (d J=2.4 Hz, 3 H, C-18 H) (Note: product is a mixture of diastereomers); IR (CHCl3) 3605, 2900 cm-1 ; MS (CI/isobutane) m/z 595 (M+1, 10%) , 401 (M+1-THP-Bn-H2O, 25%), 385 (M+1-THP-HOBn, H2O, 100%); m.p. 55°-59° C.; Anal. calcd. for C39H62O4 : 78.74, H=10.50; Found: C=78.65, H=10.54.

Workup

  1. customto quench
  2. customthe reaction
  3. customthe THF was removed in vacuo
  4. additionDistilled H2O (5 ml) was added
  5. extractionthe solution extracted 3× with 15 ml CH2Cl2
  6. washThe combined organic layers were washed with aqueous saturated NaCl solution (15 ml)
  7. dry with materialdried over anhydrous MgSO4
  8. filtrationfiltered
  9. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-662bd4764eef45d68003eb74c12b22af
Source dataset
uspto-grants-1998_11
Patent number
US05840740

Reaction notes

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