Dichloromethane → HCID 53240557, compound

HRID 422191Notes

Reaction equation

HRID 422191 reaction equation
[CH3:1][O:2][C:3]1[CH:20]=[C:19]([O:21]C)[CH:18]=[C:17]2[C:4]=1[C@H:5]1[C@H:14]([CH2:15][S:16]2(=[O:24])=[O:23])[C@:13]2([CH3:25])[C@H:8]([C:9]([CH3:27])([CH3:26])[CH2:10][CH2:11][CH2:12]2)[CH2:7][CH2:6]1.B(Br)(Br)Br.Cl[CH2:33]Cl>>[OH:21][C:19]1[CH:18]=[C:17]2[C:4]([C@@:5]3([CH3:33])[C@H:14]([CH2:15][S:16]2(=[O:24])=[O:23])[C@:13]2([CH3:25])[C@H:8]([C:9]([CH3:27])([CH3:26])[CH2:10][CH2:11][CH2:12]2)[CH2:7][CH2:6]3)=[C:3]([O:2][CH3:1])[CH:20]=1

Participants

4

Reactant 3

HCID 6344DichloromethaneHCID 25134Boron tribromideHCID 86654187HCID 86654187, compound

Product 1

HCID 53240557HCID 53240557, compoundYield 60%

Procedure

To a suspension of compound 23 (5.00 g, 12.3 mmol) in dichloromethane (20 mL) at 0° C. under argon was slowly added boron tribromide (1.0 M in DCM, 12.5 mL, 12.5 mmol). The mixture was stirred for 60 h then concentrated. The residue was dissolved in ethyl acetate (50 mL), quenched with water (250 mL) and extracted with ethyl acetate (2×200 mL). The organic layer was washed with brine (2×250 mL) then dried (MgSO4) and concentrated to afford a brown foam. The crude product was purified by column chromatography on silica gel (hexanes:ethyl acetate, 2:1) to afford compound 57 (2.90 g, 60%) as a pale solid. 1H NMR (CDCl3): δ 7.00 (d, J=2.6 Hz, 1H), 6.54 (d, J=2.5 Hz, 1H), 6.20 (s, 1H), 3.79 (s, 3H), 3.36-3.16 (m, 3H), 2.27 (d, J=11.4 Hz, 1H), 1.72-1.00 (m, 10H), 1.38 (s, 3H), 0.95 (s, 3H), 0.86 (s, 3H), 0.83 (s, 3H). 13C NMR (CDCl3): δ 159.7, 157.0, 139.3, 127.8, 105.4, 102.4, 56.2, 56.1, 53.4, 46.3, 41.9, 39.8, 39.0, 38.1, 33.7, 33.5, 21.7, 19.2, 19.1, 18.8, 17.8, 17.7. MS m/z 393 (C22H32O4S+H+).

Workup

  1. concentrationthen concentrated
  2. dissolutionThe residue was dissolved in ethyl acetate (50 mL)
  3. customquenched with water (250 mL)
  4. extractionextracted with ethyl acetate (2×200 mL)
  5. washThe organic layer was washed with brine (2×250 mL)
  6. dry with materialthen dried (MgSO4)
  7. concentrationconcentrated
  8. customto afford a brown foam
  9. customThe crude product was purified by column chromatography on silica gel (hexanes:ethyl acetate, 2:1)

Sources & evidence

ORD record
ord-78a5063b3d364f7f8e81ab9eca676f04
Source dataset
uspto-grants-2012_01
Patent number
US08101605B2

Reaction notes

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