Water → HCID 58906148, compound

HRID 1929325Notes

Reaction equation

HRID 1929325 reaction equation
CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[OH:23][C@@:24]12[CH2:32][C@@H:28]([O:29][C:30]1=[O:31])[C@H:27]([OH:33])[C@H:26]([O:34][Si:35]([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:37])[CH3:36])[CH2:25]2.O>C(Cl)Cl>[Si:35]([O:34][C@H:26]1[C:27](=[O:33])[C@H:28]2[CH2:32][C@:24]([OH:23])([C:30](=[O:31])[O:29]2)[CH2:25]1)([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:37])[CH3:36]

Participants

5

Reactant 3

HCID 962Water2×HCID 159087TriacetoxyperiodinaneHCID 11781203HCID 11781203, compound

Product 1

HCID 58906148HCID 58906148, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred suspension of Dess-Martin periodinane reagent (6.60 g, 15.5 mmol) in anhydrous CH2Cl2 (100 mL) was added compound 2 (3.86 g, 13.4 mmol). The mixture was stirred at room temperature for 18 hours, poured into water, and extracted with ethyl acetate. The organic layer was washed several times with water, dried (MgSO4), and evaporated to give an oily residue which slowly crystallized on cooling (3.67 g, 95%). TLC indicated high purity of the obtained ketone 3 which could be used in the next step without further purification. Analytical sample was obtained by recrystallization from hexane. 3: m.p. 92-95° C.; 1H NMR (400 MHz, CDCl3) δ0.040 and 0.133 (3H and 3H, each s, 2×SiCH3), 0.895 (9H, s, Si-t-Bu), 2.15 (1H, dd, J=12.4, 10.4 Hz, 2α-H), 2.42 (1H, d, J=12.5 Hz, 8α-H), 2.54 (1H, ddd, J=12.4, 9.0, 3.9 Hz, 2β-H), 2.86 (1H, ddd, J=12.5, 6.7, 3.9 Hz, 8β-H), 4.54 (1H, dd, J=10.4, 9.0 Hz, 3β-H), 4.73 (1H, d, J=6.7 Hz, 5α-H); 13C NMR (125 MHz) δ−5.6 (Si—CH3), −4.8 (Si—CH3), 18.2 [C(CH3)3], 25.6 [C(CH3)3], 42.3 (C8), 43.0 (C2), 70.3 (C3), 71.8 (C1), 78.7 (C5), 177.1 (C═O), 202.4 (C4); MS (EI) m/z (relative intensity) no M+, 271 (M+−CH3, 4), 229 (92), 201 (28), 157 (100); HRMS (ESI) exact mass calcd for C9H13O5Si (M+−t-Bu) 229.0532, measured 229.0539; Anal. Calcd for C13H22O5Si×H2O: C, 51.29, H, 7.95. Found: C, 51.09, H, 7.90.

Workup

  1. extractionextracted with ethyl acetate
  2. washThe organic layer was washed several times with water
  3. dry with materialdried (MgSO4)
  4. customevaporated
  5. customto give an oily residue which
  6. customslowly crystallized
  7. temperatureon cooling (3.67 g, 95%)
  8. customcould be used in the next step without further purification
  9. customAnalytical sample was obtained by recrystallization from hexane

Sources & evidence

ORD record
ord-d1ed061ed557463f886d11b9a78fcb59
Source dataset
uspto-grants-2012_05
Patent number
US08188064B2

Reaction notes

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