Dibah → HCID 59440099, compound

HRID 2403484Notes

Reaction equation

HRID 2403484 reaction equation
C[O:2][C:3]([C@@H:5]1[CH2:13][C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[N:6]1[C:14](=[O:34])[C:15]1[CH:20]=[C:19]([O:21][CH3:22])[C:18]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[CH:17][C:16]=1[N+:31]([O-:33])=[O:32])=O.CC(C[Al]CC(C)C)C>ClCCl.C1(C)C=CC=CC=1>[CH3:22][O:21][C:19]1[C:18]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[CH:17][C:16]([N+:31]([O-:33])=[O:32])=[C:15]([CH:20]=1)[C:14]([N:6]1[C:7]2[C:12](=[CH:11][CH:10]=[CH:9][CH:8]=2)[CH2:13][C@H:5]1[CH:3]=[O:2])=[O:34]

Participants

5

Reactant 2

HCID 16682954DibahHCID 59440167HCID 59440167, compound

Product 1

HCID 59440099HCID 59440099, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a stirred solution of the methyl ester 5 (4.4 g, 9.5 mmol) in anhydrous dichloromethane (11 mL) and toluene (33 mL) was added dibal-H (19 mL, 1.0 M in toluene) dropwise via a syringe pump in 30 minutes at −78° C. The mixture continued to be stirred at −78° C. for 3 hours and TLC (hexanes/AcOEt, 1:1.5) showed that the starting material was almost consumed. The reaction was quenched with methanol (0.4 mL) and 5% HCl (30 mL) at −78° C. Ethyl acetate (100 mL) was added and the dry ice/acetone bath was removed. The mixture was stirred at room temperature for 30 minutes and then transferred to a reparatory funnel. The aqueous layer was extracted with AcOEt twice and the combined organic layers were washed with brine, saturated sodium bicarbonate and brine, and dried over anhydrous sodium sulfate. It was filtered through celite and the solvents were removed under reduced pressure (temperature<35° C.). The residue was purified by flash chromatography (Hexanes/AcOEt, 1.5:1, 1:1, 1:1.5) to give the aldehyde 6 as a yellow solid (2.85 g, y=69%). 1H NMR (400 Hz, CDCl3): the compound appears as three distinct rotomers. δ 10.02 (s, 0.3H), 9.85 (s, 0.5H), 9.45 (s, 0.2H), 8.32-8.31 (m, 0.2H), 7.93 (s, 0.3H), 7.83 (s, 0.5H), 7.79 (s, 0.2H), 7.53-7.34 (m, 5.2H), 7.26-7.14 (m, 1.3H), 7.08 (s, 0.5H), 7.01-6.94 (m, 1H), 6.91-6.82 (m, 1H), 5.78 (d, J=8.4 Hz, 0.3H), 5.71 (d, J=8.4 Hz, 0.5H), 5.52-5.48 (m, 0.5H), 5.35-5.21 (m, 2.3H), 4.53-4.50 (m, 0.2H), 4.06 (s, 1.5H), 3.98 (s, 0.6H), 3.94 (s, 0.9H), 3.63-3.17 (m, 2H); HRMS (ESI, m/z): calc. 433.1400 (M+H)+. found 433.1387.

Workup

  1. customwas almost consumed
  2. customThe reaction was quenched with methanol (0.4 mL) and 5% HCl (30 mL) at −78° C
  3. additionEthyl acetate (100 mL) was added
  4. customthe dry ice/acetone bath was removed
  5. stirringThe mixture was stirred at room temperature for 30 minutes
  6. customtransferred to a reparatory funnel
  7. extractionThe aqueous layer was extracted with AcOEt twice
  8. washthe combined organic layers were washed with brine, saturated sodium bicarbonate and brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. filtrationIt was filtered through celite
  11. customthe solvents were removed under reduced pressure (temperature<35° C.)
  12. customThe residue was purified by flash chromatography (Hexanes/AcOEt, 1.5:1, 1:1, 1:1.5)

Sources & evidence

ORD record
ord-ac25bc9c6c0446798d408b01dc35a081
Source dataset
uspto-grants-2014_08
Patent number
US08802667B2

Reaction notes

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