Diisobutylaluminum hydride → HCID 86698559, compound

HRID 1846153Notes

Reaction equation

HRID 1846153 reaction equation
[CH3:1][N:2]1[C:6]2=[N:7][C:8]([CH3:23])=[C:9]([C:19](OC)=[O:20])[C:10]([O:11][S:12]([C:15]([F:18])([F:17])[F:16])(=[O:14])=[O:13])=[C:5]2[CH2:4][CH2:3]1.CC(C[AlH]CC(C)C)C.C(C(C(C([O-])=O)O)O)([O-])=O.[K+].[Na+]>ClCCl>[F:18][C:15]([F:16])([F:17])[S:12]([O:11][C:10]1[C:9]([CH2:19][OH:20])=[C:8]([CH3:23])[N:7]=[C:6]2[N:2]([CH3:1])[CH2:3][CH2:4][C:5]=12)(=[O:14])=[O:13]

Participants

5

Reactant 3

HCID 14487Diisobutylaluminum hydrideHCID 9855836Potassium sodium tartarateHCID 86698560HCID 86698560, compound

Product 1

HCID 86698559HCID 86698559, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 169.7 mg of methyl ester 29 in 2 mL of dichloromethane was added 1.43 mL of DIBAL-H (1M in toluene, 3 eq) dropwise at −78° C. under Ar protection. After addition, the reaction mixture was stirred at the same temperature and stirred for additional 2 h then 5 mL of aqueous saturated sodium potassium tartrate was added by syringe. The reaction mixture was allowed to warm to room temperature and stirred for additional 4 h. After separation, the aqueous layer was extracted with three portions of 5 mL of dichloromethane. The combined organic layer was washed with brine and dried over magnesium sulfate. After the solvent was removed, the residue was purified by flash chromatography on a silica gel column (15×2 cm). Elution with 1:2 EtOAc-hexanes gave product 30 as white solid: yield 148 mg, (95%). Silica gel TLC Rf 0.20 (1:1 EtOAc-hexanes); 1H NMR (CDCl3, ppm): δ 1.72 (br s, 1H), 2.52 (s, 3H), 2.96 (s, 3H), 3.08 (t, J=8.4 Hz, 2H), 3.54 (t, J=8.4 Hz, 2H), 4.58 (s, 2H). 13C NMR (CDCl3, ppm): δ 22.01, 23.97, 32.29, 51.78, 76.68, 111.48, 114.08, 149.79, 159.93, 164.67; HRMS (ESI+) calculated for C11H13N2O4SF3 (M+H+) 327.0621. found 327.0622.

Workup

  1. additionAfter addition
  2. stirringstirred for additional 2 h
  3. stirringstirred for additional 4 h
  4. customAfter separation
  5. extractionthe aqueous layer was extracted with three portions of 5 mL of dichloromethane
  6. washThe combined organic layer was washed with brine
  7. dry with materialdried over magnesium sulfate
  8. customAfter the solvent was removed
  9. customthe residue was purified by flash chromatography on a silica gel column (15×2 cm)
  10. washElution with 1:2 EtOAc-hexanes

Sources & evidence

ORD record
ord-c5b83e3ad9db44569b7e3c0406284402
Source dataset
uspto-grants-2015_02
Patent number
US08952025B2

Reaction notes

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