Tetrabutylammonium Fluoride → HCID 10053347, compound

HRID 363838Notes

Reaction equation

HRID 363838 reaction equation
[CH2:1]([O:8][C@@H:9]1[CH2:38][C@@H:37]2[C@:32]([CH3:46])([CH2:33][CH2:34][C@H:35]([O:39][CH:40]3[CH2:45][CH2:44][CH2:43][CH2:42][O:41]3)[CH2:36]2)[C@@H:31]2[C@@H:10]1[C@H:11]1[C@:28]([CH3:47])([CH2:29][CH2:30]2)[C@@H:14]([C@H:15]([CH3:27])[CH2:16][CH2:17][CH2:18][O:19][Si](C(C)(C)C)(C)C)[CH2:13][CH2:12]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1COCC1>[CH2:1]([O:8][C@@H:9]1[CH2:38][C@@H:37]2[C@:32]([CH3:46])([CH2:33][CH2:34][C@H:35]([O:39][CH:40]3[CH2:45][CH2:44][CH2:43][CH2:42][O:41]3)[CH2:36]2)[C@@H:31]2[C@@H:10]1[C@H:11]1[C@:28]([CH3:47])([CH2:29][CH2:30]2)[C@@H:14]([C@H:15]([CH3:27])[CH2:16][CH2:17][CH2:18][OH:19])[CH2:13][CH2:12]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 10462082HCID 10462082, compound

Product 1

HCID 10053347HCID 10053347, compoundYield 90.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Compound 2007 (0.0527 g, 0.079 mmol) in anhydrous THF (4 ml) under Ar was treated with tetrabutylammonium fluoride (TBAF) (0.237 ml, 1M in THF, 0.237 mmol). The solution was stirred until no starting material remained by TLC. The solvent was removed in vacuo, the residue taken up in 5 ml CH2Cl2, washed with 5 ml aqueous saturated NaHCO3 solution, and the aqueous layer was extracted 2x with 5 ml CH2Cl2. The combined organic layers were dried over anhydrous MgSO4, filtered, and the solvent removed in vacuo. Flash chromatography (SiO2, 8:1 hexanes:EtOAc) gave compound 2008 (0.0395 g, 90%) as a white solid foam. 1H NMR (500 MHz, CDCl3) δ: 7.35-7.34 (m, 5H, benzyl Ar--H), 4.71-4.69 (m, 1H, THP ether methine H), 4.585 (d, J=11.8 Hz, 1/2H, benzyl-CH2), 4.58 (d, J=11.8 Hz, 1/2H, benzyl-CH2), 4.315 (d, J=12.0 Hz, 1/2H, benzyl-CH2), 4.29 (d, J=12.0 Hz, 1/2H, benzyl-CH2), 3.94-3.90 (m, 1H, THP OCH2), 3.62-3.58 (m, 3H, C-24 H & THP OCH2), 3.50-3.48 (m, 1H, C-3 H), 3.45 (s, 1H, 7-H), 0.92 (d, J=6.6 Hz, 3H, C-21 H), 0.81 (s, 3H, C-19 H), 0.63 (s, 3H, C-18H) (Note: product is a mixture of diastereomers); IR (CHCl3) 3600, 2900 cm-1 ; MS (CI/isobutane) m/z 554 (M+1, 2%), 361 (M+1-THP-HOBn, 42%), 343 (M+1-THP-HPBn, H2O, 100%); m.p. 52°-56° C.; Anal. calcd. for C36H56O4 : C=78.21, H=10.21; Found: C=77.93, H=10.39.

Workup

  1. customThe solvent was removed in vacuo
  2. washwashed with 5 ml aqueous saturated NaHCO3 solution
  3. extractionthe aqueous layer was extracted 2x with 5 ml CH2Cl2
  4. dry with materialThe combined organic layers were dried over anhydrous MgSO4
  5. filtrationfiltered
  6. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-866bae63dce144e5816736724e38ae74
Source dataset
uspto-grants-1999_02
Patent number
US05874597

Reaction notes

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