Borane → HCID 58593382, compound

HRID 916992Notes

Reaction equation

HRID 916992 reaction equation
[C:1]([C:5]1[CH:18]=[C:17]([S:19][C:20]([S:23][C:24]2[CH:29]=[C:28]([C:30]([CH3:33])([CH3:32])[CH3:31])[C:27]([OH:34])=[C:26]([C:35]([CH3:38])([CH3:37])[CH3:36])[CH:25]=2)([CH3:22])[CH3:21])[CH:16]=[C:15]([C:39]([CH3:42])([CH3:41])[CH3:40])[C:6]=1[O:7][CH2:8][CH2:9][C@H:10]([OH:14])[C:11](O)=[O:12])([CH3:4])([CH3:3])[CH3:2].B>C1COCC1>[C:1]([C:5]1[CH:18]=[C:17]([S:19][C:20]([S:23][C:24]2[CH:29]=[C:28]([C:30]([CH3:33])([CH3:32])[CH3:31])[C:27]([OH:34])=[C:26]([C:35]([CH3:38])([CH3:37])[CH3:36])[CH:25]=2)([CH3:22])[CH3:21])[CH:16]=[C:15]([C:39]([CH3:42])([CH3:41])[CH3:40])[C:6]=1[O:7][CH2:8][CH2:9][C@H:10]([OH:14])[CH2:11][OH:12])([CH3:4])([CH3:3])[CH3:2]

Participants

4

Reactant 2

HCID 6331BoraneHCID 58593378HCID 58593378, compound

Product 1

HCID 58593382HCID 58593382, compoundYield 47.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A 100 mL round bottom flask equipped with a nitrogen adapter and temperature probe was charged with 1.42 g (2.3 mmol, 1 eq) of 4-{2,6-di-tert-butyl-4-[1-(3,5-di-tert-butyl-4-hydroxy-phenylsulfanyl)-1-methyl-ethylsulfanyl]-phenoxy}-2(S)-hydroxy-butyric acid (Ex-10C), 25 mL THF and cooled to 0° C. The solution was treated with 6.9 mL (6.9 mmol, 3 eq) of 1.0 M borane in THF, warmed to 25° C. and monitored by HPLC. After stirring 6 hours at 25° C., the reaction was cooled using an ice bath, quenched with 15 mL of methanol and concentrated under reduced pressure. The residue was purified by silica gel chromatography (20% EtOAc/hexanes gradient to 80% EtOAc/hexanes) and dried in vacuo to yield 660 mg (1.1 mmol, 47% yield) of 4-{2,6-di-tert-butyl-4-[1-(3,5-di-tert-butyl-4-hydroxy-phenylsulfanyl)-1-methyl-ethylsulfanyl]-phenoxy}-butane-1,2(S)-diol as a white solid, mp 110–112° C. 1H NMR (300 MHz, CDCl3) δ: 7.56 (s, 2H), 7.46 (s, 2H), 5.38 (s, 1H), 3.86–4.06 (m, 3H), 3.71–3.78 (m, 1H), 3.52–3.60 (m, 1H), 2.54 (d, 1H, J=4.08 Hz), 1.97–2.12 (m, 2H), 1.92 (t, 1H, J=6.19 Hz), 1.46 (s, 6H), 1.46 (s, 18H), 1.45 (s, 18H). Anal. calcd for C35H56O4S2: C69.49, H9.33, S10.60; found: C68.86, H9.25, S10.39HRMS (EI+) m/z+Na: calc. 627.3518; found 627.3539.

Workup

  1. customA 100 mL round bottom flask equipped with a nitrogen adapter
  2. temperaturewarmed to 25° C.
  3. temperaturethe reaction was cooled
  4. customquenched with 15 mL of methanol
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by silica gel chromatography (20% EtOAc/hexanes gradient to 80% EtOAc/hexanes)
  7. customdried in vacuo

Sources & evidence

ORD record
ord-e33228ae3f154ff1a54c83923b43e403
Source dataset
uspto-grants-2007_09
Patent number
US07271274B2

Reaction notes

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