Water → HCID 11558955, compound

HRID 1929326Notes

Reaction equation

HRID 1929326 reaction equation
[Si:1]([O:8][C@H:9]1[C:15](=[O:16])[C@H:14]2[CH2:17][C@:11]([OH:19])([C:12](=[O:18])[O:13]2)[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[OH2:20].N1[CH:26]=[CH:25]C=CC=1>C(OC(=O)C)(=O)C.CCCCCC.C(OCC)(=O)C>[C:25]([O:19][C@@:11]12[CH2:17][C@@H:14]([O:13][C:12]1=[O:18])[C:15](=[O:16])[C@H:9]([O:8][Si:1]([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2])[CH2:10]2)(=[O:20])[CH3:26]

Participants

6

Reactant 3

HCID 962WaterHCID 1049PyridineHCID 58906148HCID 58906148, compound

Product 1

HCID 11558955HCID 11558955, compoundYield 81%

Reagents, catalysts & solvents 2

HCID 7918Acetic AnhydrideSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

A solution of hydroxy ketone 3 (1.64 g, 5.8 mmol) in anhydrous pyridine (12 mL) and acetic anhydride (5.5 mL) was stirred for 3 hours at room temperature. The reaction mixture was then poured into water and extracted with ethyl acetate. The organic layer was washed with saturated NaHCO3, saturated CuSO4 and water, dried (MgSO4), and evaporated to give an oily residue which was dissolved in hexane/ethyl acetate (8:2) and filtered through short path of silica gel. Evaporation of solvents gave pure crystalline acetate 4 (1.51 g, 81%). Analytical sample was obtained by recrystallization from hexane/ethyl acetate. 4: m.p. 134-7° C.; [α]24D−78° (c 1.00 CHCl3); 1H NMR (400 MHz, CDCl3) δ0.046 and 0.141 (3H and 3H, each s, 2×SiCH3), 0.901 (9H, s, Si-t-Bu), 2.17 (3H, s, CH3CO), 2.28 (1H, dd, J=12.2, 10.4 Hz, 2α-H), 2.32 (1H, d, J=12.1 Hz, 8α-H), 2.65 (1H, ddd, J=12.2, 8.8, 3.9 Hz, 2β-H), 3.56 (1H, ddd ,J=12.1, 6.9, 3.9 Hz, 8β-H), 4.58 (1H, dd, J=10.4, 8.8 Hz, 3β-H), 4.80 (1H, d, J=6.9 Hz, 5α-H); 13C NMR (125 MHz) δ−5.8 (Si—CH3), −4.9 (Si—CH3), 18.2 [C(CH3)3], 20.9 (CH3—C═O), 25.6 [C(CH3)3], 38.3 (C8), 40.3 (C2), 70.4 (C3), 75.3 (C1), 78.4 (C5), 169.1 (CH3—C═O), 171.5 (C═O), 201.8 (C4); MS (EI) m/z (relative intensity) 328 (M+, 6), 271 (100), 256 (38), 229 (54), 211 (53); HRMS (ESI) exact mass calcd for C11H15O6Si (M+−t-Bu) 271.0638, measured 271.0646; Anal. Calcd for C15H24O6Si: C, 54.86, H, 7.37. Found: C, 54.88, H, 7.37.

Workup

  1. extractionextracted with ethyl acetate
  2. washThe organic layer was washed with saturated NaHCO3, saturated CuSO4 and water
  3. dry with materialdried (MgSO4)
  4. customevaporated
  5. customto give an oily residue which
  6. filtrationfiltered through short path of silica gel
  7. customEvaporation of solvents

Sources & evidence

ORD record
ord-5bb48e9174ca45df9a91d2a7493d9561
Source dataset
uspto-grants-2012_05
Patent number
US08188064B2

Reaction notes

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