Citric Acid → HCID 89646971, compound

HRID 868892Notes

Reaction equation

HRID 868892 reaction equation
[CH3:1][C:2]1([CH3:17])[O:15][C:6]2=[N:7][C:8]([C:11]([F:14])([F:13])[F:12])=[CH:9][CH:10]=[C:5]2[C:4](=O)[CH2:3]1.[CH3:18][C:19]([S@:22]([NH2:24])=[O:23])([CH3:21])[CH3:20].[BH4-].[Na+].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>CC1CCCO1.C(O[Ti](OCC)(OCC)OCC)C>[CH3:1][C:2]1([CH3:17])[O:15][C:6]2=[N:7][C:8]([C:11]([F:14])([F:13])[F:12])=[CH:9][CH:10]=[C:5]2[C@H:4]([NH:24][S:22]([C:19]([CH3:21])([CH3:20])[CH3:18])=[O:23])[CH2:3]1

Participants

7

Reactant 4

HCID 311Citric AcidHCID 4311764Sodium borohydrideHCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 14043515HCID 14043515, compound

Product 1

HCID 89646971HCID 89646971, compoundYield 99%

Reagents, catalysts & solvents 2

HCID 178477244HCID 178477244, compoundCatalystHCID 73012-MethyltetrahydrofuranSolvent2×

Conditions

Temperature
-10 °C

Procedure

A solution of Example 62B (1.52 g, 6.20 mmol), (R)-2-methylpropane-2-sulfinamide (1.127 g, 9.30 mmol), 2-methyltetrahydrofuran (20 mL), and tetraethoxytitanium (5.20 mL, 24.8 mmol) was heated to 70° C. After 3 hours the solution was cooled to −10° C. and sodium borohydride (0.469 g, 12.4 mmol) was added. The mixture was warmed to room temperature, stirred for 2 hours then cooled to 0° C. and 10% aqueous citric acid (50 mL) was added. The mixture was stirred vigorously overnight then diluted with methyltetrahydrofuran (300 mL). The layers were separated and the organic extract was washed with water and brine, dried (Na2SO4), filtered, and concentrated. Purification by flash chromatography (SiO2, 20-100% hexane/ethyl acetate gradient) provided the title compound (2.14 g, 6.11 mmol, 99% yield). MS (DCI+) m/z 349 (M+H)+.

Workup

  1. temperatureThe mixture was warmed to room temperature
  2. temperaturethen cooled to 0° C.
  3. stirringThe mixture was stirred vigorously overnight
  4. customThe layers were separated
  5. extractionthe organic extract
  6. washwas washed with water and brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification by flash chromatography (SiO2, 20-100% hexane/ethyl acetate gradient)

Sources & evidence

ORD record
ord-d0e48e696e45438d90bc676d7f6136c9
Source dataset
uspto-grants-2015_03
Patent number
US08969325B2

Reaction notes

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