Hydrochloric Acid → HCID 10080608, compound

HRID 626090Notes

Reaction equation

HRID 626090 reaction equation
Cl(O)(=O)(=O)=O.[CH3:6][C@H:7]1[C:11](=[O:12])[O:10][C@@H:9]2[CH2:13][CH:14]=[CH:15][C@H:8]12.[OH-:16].[Na+].[BH4-].[Na+].Cl.[Na+].[Cl-]>C1COCC1.O.C1COCC1.[Hg](OC(C)=O)OC(C)=O>[OH:16][C@H:14]1[CH2:13][C@H:9]2[O:10][C:11](=[O:12])[C@H:7]([CH3:6])[C@H:8]2[CH2:15]1

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 5234Sodium ChlorideHCID 14798Sodium HydroxideHCID 24247Perchloric Acid2×HCID 4311764Sodium borohydrideHCID 11378527HCID 11378527, compound

Product 1

HCID 10080608HCID 10080608, compoundYield 64%

Reagents, catalysts & solvents 3

HCID 16683746DiacetyloxymercuryCatalyst2×HCID 8028TetrahydrofuranSolventHCID 21881883Oxolane--water (1/1)Solvent2×

Conditions

Temperature
0 °C

Procedure

To a ice-cold yellow solution of Hg(OAc)2 (1.45 g, 4.57 mmol) in THF:H2O (2.5:1 ratio, 23 mL) was added perchloric acid (˜0.7 mL) until the solution became colorless. A solution of lactone 116 (350 mg, 2.54 mmol) in THF (7 mL) was then added at 0° C. and the reaction was stirred for 1 h. Additional Hg(OAc)2 (646 mg, 2.03 mmol) similarly pretreated with perchloric acid in THF:H2O (2.5:1, 10 mL) was added and stirring was continued for 2 h at 0° C. The pH of the mixture was then adjusted to ˜10 by addition of a 1M aqueous NaOH solution. Stirring was then continued for 1 h at room temperature. The solution was cooled to 0° C. and NaBH4 (145 mg, 3.81 mmol) was added in small portions. After 1 h, the reaction mixture was acidified to pH=2 with concentrated HCl and stirring was continued for 1 h. The reaction solution was saturated with NaCl, and the aqueous phase extracted several times with EtOAc. The combined organic phase was dried (Na2SO4), filtered, and concentrated under vacuum. The residue was purified by column chromatography on silica gel using 2% MeOH in CH2Cl2 to yield alcohol 117 (252 mg, 64%) as a colorless oil. TLC: Rf=0.31 (CHCl3/MeOH=9/1); [α]D20+53.5 (c 1.0, CHCl3); 1H NMR (CDCl3, 400 MHz) δ 4.98 (dt, J=8.0, 14.9 Hz, 1H), 4.55 (m, 1H), 2.69 (qd, J=3.9, 7.6 Hz, 1H), 2.58 (m, 1H), 2.55 (m, 1H), 2.09 (d, J=15.0 Hz, 1H), 1.94 (m, 2H), 1.83 (m, 1H), 1.26 (d, J=7.6 Hz, 3H); 13C NMR (CDCl3, 100 MHz) δ 181.0, 83.8, 74.6, 51.2, 45.5, 43.9, 41.3, 18.4.

Workup

  1. additionwas added
  2. stirringstirring
  3. waitwas continued for 2 h at 0° C
  4. stirringStirring
  5. waitwas then continued for 1 h at room temperature
  6. waitAfter 1 h
  7. stirringstirring
  8. waitwas continued for 1 h
  9. extractionthe aqueous phase extracted several times with EtOAc
  10. dry with materialThe combined organic phase was dried (Na2SO4)
  11. filtrationfiltered
  12. concentrationconcentrated under vacuum
  13. customThe residue was purified by column chromatography on silica gel using 2% MeOH in CH2Cl2

Sources & evidence

ORD record
ord-dbdb1bec67ed485f8be783fb1e5281b6
Source dataset
uspto-grants-2016_04
Patent number
US09309213B2

Reaction notes

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