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

HRID 422133Notes

Reaction equation

HRID 422133 reaction equation
C[O:2][C:3]1[CH:20]=[C:19]([CH3:21])[CH:18]=[C:17]2[C:4]=1[C@@:5]1([CH3:25])[C@H:14]([CH2:15][S:16]2)[C@:13]2([CH3:22])[C@H:8]([C:9]([CH3:24])([CH3:23])[CH2:10][CH2:11][CH2:12]2)[CH2:7][CH2:6]1.B(Br)(Br)Br>C(Cl)Cl>[CH3:25][C@@:5]12[CH2:6][CH2:7][C@@H:8]3[C@:13]([CH3:22])([CH2:12][CH2:11][CH2:10][C:9]3([CH3:23])[CH3:24])[C@H:14]1[CH2:15][S:16][C:17]1[C:4]2=[C:3]([OH:2])[CH:20]=[C:19]([CH3:21])[CH:18]=1

Participants

4

Reactant 2

HCID 25134Boron tribromideHCID 53241772(1R,10R,11S,16S)-3-methoxy-1,5,11,15,15-pentamethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene

Product 1

HCID 53241773(1R,10R,11S,16S)-1,5,11,15,15-pentamethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-ol

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (1R,10R,11S,16S)-3-methoxy-1,5,11,15,15-pentamethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene (Compound No. 14) (1.16 g, 3.23 mmol) in CH2Cl2 (100 mL) was added BBr3 (1.0 M in CH2Cl2, 9.70 mL, 9.70 mmol) dropwise at 0° C., and the resulting mixture stirred at room temperature overnight, then concentrated to dryness. Water (20 mL) was added at 0° C., followed by EtOAc (100 mL). The organic layer was separated, washed with brine (2×20 mL), dried (Na2SO4), and concentrated. Purification by chromatography on silica gel (Hexanes/EtOAc, 9:1) gave (1R,10R,11S,16S)-1,5,11,15,15-pentamethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-ol (Compound No. 15) (0.88 g, 79%) as a white solid. 1H NMR (CDCl3): δ 6.50 (s, 1H), 6.15 (s, 1H), 4.60 (s, 1H), 3.38 (m, 1H), 2.90 (m, 1H), 2.78 (m, 1H), 2.18 (s, 3H), 1.84-1.42 (m, 9H), 1.40 (s, 3H), 1.20-1.00 (m, 2H), 0.98 (s, 3H), 0.89 (s, 3H), 0.89 (s, 3H). MS m/z 343 (C22H32OS−H+).

Workup

  1. concentrationconcentrated to dryness
  2. additionWater (20 mL) was added at 0° C.
  3. customThe organic layer was separated
  4. washwashed with brine (2×20 mL)
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated
  7. customPurification by chromatography on silica gel (Hexanes/EtOAc, 9:1)

Sources & evidence

ORD record
ord-3b22b078ccf145b2b540588b92176142
Source dataset
uspto-grants-2012_01
Patent number
US08101605B2

Reaction notes

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