Boron tribromide → (1R,10R,11S,16S)-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3,5-diol

HRID 422138Notes

Reaction equation

HRID 422138 reaction equation
C[O:2][C:3]1[CH:20]=[C:19]([O:21]C)[CH:18]=[C:17]2[C:4]=1[C@@:5]1([CH3:26])[C@H:14]([CH2:15][S:16]2)[C@:13]2([CH3:23])[C@H:8]([C:9]([CH3:25])([CH3:24])[CH2:10][CH2:11][CH2:12]2)[CH2:7][CH2:6]1.B(Br)(Br)Br>C(Cl)Cl>[CH3:26][C@@:5]12[CH2:6][CH2:7][C@@H:8]3[C@:13]([CH3:23])([CH2:12][CH2:11][CH2:10][C:9]3([CH3:24])[CH3:25])[C@H:14]1[CH2:15][S:16][C:17]1[C:4]2=[C:3]([OH:2])[CH:20]=[C:19]([OH:21])[CH:18]=1

Participants

4

Reactant 2

HCID 25134Boron tribromideHCID 53241775(1R,10R,11S,16S)-3,5-dimethoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene

Product 1

HCID 53241885(1R,10R,11S,16S)-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3,5-diol

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (1R,10R,11S,16S)-3,5-dimethoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 22) (3.75 g, 10 mmol) in CH2Cl2 (200 mL) was added BBr3 (1.0 M in CH2Cl2, 60 mL, 60 mmol) dropwise at 0° C., and the resulting mixture was stirred at room temperature for 48 h, then concentrated to dryness. Water (100 mL) was added at 0° C., followed by EtOAc (500 mL). The organic layer was separated, washed with brine (2×50 mL), dried (Na2SO4), and concentrated. Purification by chromatography on silica gel (Hexanes/EtOAc, 3:1) followed by dilution with MeOH, concentration and trituration with water gave (1R,10R,11S,16S)-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3,5-diol (Compound No. 26) (620 mg, 18%) as an off-white solid. 1H NMR (CDCl3): δ 6.18 (d, 1H), 5.90 (d, 1H), 4.70 (s, 1H), 4.42 (s, 1H), 3.30 (m, 1H), 2.90 (m, 1H), 2.76 (m, 1H), 1.84-1.40 (m, 8H), 1.39 (s, 3H), 1.20-1.00 (m, 2H), 0.96 (s, 3H), 0.95 (m, 1H), 0.85 (s, 3H), 0.85 (s, 3H). MS m/z 345 (C21H30O2S−H+).

Workup

  1. concentrationconcentrated to dryness
  2. additionWater (100 mL) was added at 0° C.
  3. customThe organic layer was separated
  4. washwashed with brine (2×50 mL)
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated
  7. customPurification by chromatography on silica gel (Hexanes/EtOAc, 3:1)
  8. concentrationfollowed by dilution with MeOH, concentration and trituration with water

Sources & evidence

ORD record
ord-3865b3e1d616441c906fe126389c8cfb
Source dataset
uspto-grants-2012_01
Patent number
US08101605B2

Reaction notes

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