Acetic Anhydride → HCID 86698563, compound

HRID 1846156Notes

Reaction equation

HRID 1846156 reaction equation
[CH:1]([O:3][C:4]1[C:5]([C:15]#[C:16][C@@:17]([O:35]CC2C=CC=CC=2)([CH3:34])[CH2:18][CH2:19][CH2:20][C@H:21]([CH3:33])[CH2:22][CH2:23][CH2:24][C@H:25]([CH3:32])[CH2:26][CH2:27][CH2:28][CH:29]([CH3:31])[CH3:30])=C2CCN(C)C2=[N:8][C:9]=1[CH3:10])=[O:2].[CH3:43]C(C[AlH]CC(C)C)C.[CH2:52]([N:54]([CH2:57][CH3:58])[CH2:55][CH3:56])C.C(OC(=O)C)(=O)C>C(Cl)Cl.CN(C1C=CN=CC=1)C>[C:1]([O:3][C:4]1[C:5]([CH2:15][CH2:16][C@@:17]([OH:35])([CH3:34])[CH2:18][CH2:19][CH2:20][C@H:21]([CH3:33])[CH2:22][CH2:23][CH2:24][C@H:25]([CH3:32])[CH2:26][CH2:27][CH2:28][CH:29]([CH3:31])[CH3:30])=[C:56]2[CH2:58][CH2:57][N:54]([CH3:52])[C:55]2=[N:8][C:9]=1[CH3:10])(=[O:2])[CH3:43]

Participants

7

Reactant 4

HCID 7918Acetic AnhydrideHCID 8471TriethylamineHCID 14487Diisobutylaluminum hydrideHCID 86698564HCID 86698564, compound

Product 1

HCID 86698563HCID 86698563, compound

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 25 mg of formate ester 33 in 2 mL of CH2Cl2 was added 220 μL (1M in toluene, 5 eq) of DIBAL-H at −78° C. The reaction mixture was stirred at the same temperature for 1.5 h then 300 μL of triethylamine and 150 μL of acetic anhydride and catalytic amount of DMAP was added. The resulting reaction mixture was allowed to warm to room temperature and stirred for 24 h. The reaction was quenched with 2 mL of aqueous saturated ammonium chloride and extracted with three portions of 5-mL of ethyl acetate. The combined organic layer was washed with brine, dried (Na2SO4) and concentrated under diminished pressure. The residue was purified by flash chromatography on a silica gel column (20×1.7 cm). Elution with 6:100 EtOAc-hexanes gave the product 34 as yellowish oil: yield 20 mg, (78%); Silica gel TLC Rf 0.48 (1:4 EtOAc-hexanes); 1H NMR (C6H6): δ 0.87-0.93 (m, 12H), 1.02-1.99 (m, 25H), 1.52 (s, 3H), 1.95 (s, 3H), 2.37 (s, 3H), 2.49 (t, J=8.0 Hz, 2H), 2.67 (s, 3H), 4.76 (dd, J=11.6, 55.2 Hz, 2H), 7.06-7.20 (m, 3H), and 7.44 (d, J=7.6 Hz, 2H); HRMS (ESI+) calculated for C38H56N2O3 (M+H+) 589.4364. found 589.4383.

Workup

  1. customThe resulting reaction mixture
  2. stirringstirred for 24 h
  3. customThe reaction was quenched with 2 mL of aqueous saturated ammonium chloride
  4. extractionextracted with three portions of 5-mL of ethyl acetate
  5. washThe combined organic layer was washed with brine
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated under diminished pressure
  8. customThe residue was purified by flash chromatography on a silica gel column (20×1.7 cm)
  9. washElution with 6:100 EtOAc-hexanes

Sources & evidence

ORD record
ord-e3a0aa1d331b4d819f7e66248ca0bdfd
Source dataset
uspto-grants-2015_02
Patent number
US08952025B2

Reaction notes

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