Water → HCID 10837770, compound

HRID 1016270Notes

Reaction equation

HRID 1016270 reaction equation
[C:1]([O:4][C@H:5]1[C@H:10]([CH2:11][CH:12]=[CH2:13])[CH2:9][C@H:8]2[C@H:14]3[C@H:23]([CH2:24][CH2:25][C@:6]12[CH3:7])[C:22]1[CH:21]=[CH:20][C:19]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[CH:18][C:17]=1[CH2:16][CH2:15]3)(=[O:3])[CH3:2].B.C1C[O:38]CC1.C[N+]([O-])(C)C.O>COCCOCCOC.C1COCC1>[C:1]([O:4][C@H:5]1[C@H:10]([CH2:11][CH2:12][CH2:13][OH:38])[CH2:9][C@H:8]2[C@H:14]3[C@H:23]([CH2:24][CH2:25][C@:6]12[CH3:7])[C:22]1[CH:21]=[CH:20][C:19]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[CH:18][C:17]=1[CH2:16][CH2:15]3)(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 962WaterHCID 1145Trimethylamine oxideHCID 2723981Borane;tetrahydrofuranHCID 70118134HCID 70118134, compound

Product 1

HCID 10837770HCID 10837770, compoundYield 81.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8150DiglymeSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 629 mg (1.41 mmol) of 29 in anhydrous diglyme (21 mL) was stirred at 0° C. as 1.49 mmol of borane-THF (1.49 mL of a 1 M solution in THF) was added. Reaction was stirred at 0° C. for ½ h the allowed to warm to rt and stir for 2 h. To this was added 660 mg (5.96 mmol) of trimethylamine oxide and reaction was stirred and heated at 150° C. for 2 h, cooled to rt, poured into H2O (150 mL) and extracted with CH2Cl2 (3×, 100 mL). Combined organic extracts were washed with 10% sodium metabisulfite (70 mL), H2O (70 mL), dried over Na2SO4 and concentrated in vacuo. Purification of the residue by flash chromatography on a 3×22 cm column of silica gel using hexanes/EtOAc (1.5:1) as eluent gave 530 mg (81%) of 30 as a white solid. Data for 30: TLC, T-6, Rf0.34. 1H NMR (500 MHz, CDCl3) δ 0.83 (s, 3H, H-18), 2.09 (s, 3H, Oac), 2.85 (m, 2H, H-6), 3.85 (t, 2H, J=5.7 Hz, —CH2O—), 4.63 (d, 1H, J=7.8 Hz, H-17α), 5.04 (s, 2H, benzylic), 6.72 (d, 1H, J=2.6 Hz, H-4), 6.78 (dd, 1H, J=8.2, 2.6 Hz, H-2), 7.19 (d, 1H, J=2.6 Hz, H-1), 7.31-7.44 (m, 5H, Ar—H); HRMS (ES) calcd for C30H38O4Na (M+Na+) m/e 485.2668, found m/e 485.2679.

Workup

  1. additionwas added
  2. customReaction
  3. temperatureto warm to rt
  4. stirringstir for 2 h
  5. additionTo this was added
  6. stirringwas stirred
  7. temperatureheated at 150° C. for 2 h
  8. temperaturecooled to rt
  9. extractionextracted with CH2Cl2 (3×, 100 mL)
  10. washCombined organic extracts were washed with 10% sodium metabisulfite (70 mL), H2O (70 mL)
  11. dry with materialdried over Na2SO4
  12. concentrationconcentrated in vacuo
  13. customPurification of the residue by flash chromatography on a 3×22 cm column of silica gel

Sources & evidence

ORD record
ord-e2c208558089403f9521fd6cd951b0f6
Source dataset
uspto-grants-2002_11
Patent number
US06476012B2

Reaction notes

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