Acetic Anhydride → HCID 67043142, compound

HRID 1258140Notes

Reaction equation

HRID 1258140 reaction equation
[OH:1][C@:2]([CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])([CH2:13][C:14]([O:16][CH3:17])=[O:15])[C:3]([O:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)=[O:4].[C:23](OC(=O)C)(=[O:25])[CH3:24].CCOC(C)=O>N1C=CC=CC=1.O>[C:23]([O:1][C@:2]([CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])([CH2:13][C:14]([O:16][CH3:17])=[O:15])[C:3]([O:5][CH2:6][C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1)=[O:4])(=[O:25])[CH3:24]

Participants

6

Reactant 3

HCID 7918Acetic Anhydride2×HCID 8857Ethyl AcetateHCID 24879670HCID 24879670, compound

Product 1

HCID 67043142HCID 67043142, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1049PyridineSolvent

Procedure

To a solution of tertiary alcohol 77 (33.0 mg, 0.109 mmol, 1.00 equiv) in dry pyridine (500 μL) at 0° C. was added acetic anhydride (114 μL, 1.09 mmol, 10.0 equiv) and N,N-dimethylaminopyridine (DMAP) (3.0 mg, 0.0246 mmol, 0.23 equiv). The solution was then stirred at 23° C. for 17 h at which time further DMAP (13.0 mg, 1.09 mmol, 1.00 equiv) and acetic anhydride (22 μL, 0.21 mmol, 1.9 equiv) were added. After 1 h the solution was diluted with H2O (10 mL) and extracted with CH2Cl2 (3×10 mL). The combined organic extracts were washed with 0.1M aqueous CuSO4 soln, dried over MgSO4, and concentrated by rotary evaporation to yield a dark red oil. Purification by silica gel column chromatography (5:1 hexanes:EtOAc) provided S11 (28.1 mg, 74%) as a colorless oil. Rf=0.32 (5:1 hexanes:EtOAc); 1H NMR (500 MHz, CDCl3) δ 7.35 (m, 5H, ArH), 5.14 (m, 2H, ArCH2), 5.00 (tt, 1H, J=7.5, 1.3 Hz, vinyl H), 3.64 (s, 3H, CO2CH3), 3.27 (d, 1H, J=14.7 Hz, C(O)CH2), 2.96 (d, 1H, J=14.7 Hz, C(O)CH2), 2.80 (dd, 1H, J=14.6, 7.6 Hz, CHCH2), 2.69 (dd, 1H, J=14.6, 7.6 Hz, CHCH2), 2.06 (s, 3H, C(O)CH3), 1.67 (s, 3H, CCH3), 1.56 (s, 3H, CCH3); 13C NMR (125 MHz, CDCl3) δ 170.34, 170.10, 169.79, 137.21, 135.45, 128.64, 128.50, 128.46, 115.89, 80.51, 67.48, 51.85, 37.41, 34.35, 26.11, 21.09, 18.00; IR (neat film) 3067 (w), 2955 (w), 1746 (s), 1441 (m), 1371 (m), 1227 (m); LRMS (ESI) calcd for C19H24O6Na (M++Na) 371.16; observed 371.00.

Workup

  1. additionwere added
  2. extractionextracted with CH2Cl2 (3×10 mL)
  3. washThe combined organic extracts were washed with 0.1M aqueous CuSO4 soln
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated by rotary evaporation
  6. customto yield a dark red oil
  7. customPurification by silica gel column chromatography (5:1 hexanes:EtOAc)
  8. customprovided S11 (28.1 mg, 74%) as a colorless oil

Sources & evidence

ORD record
ord-8cea44655b614818ad62a05a40de038a
Source dataset
uspto-grants-2013_06
Patent number
US08466142B2

Reaction notes

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