Phosphorus trichloride → TRANS 5-(t-BUTYLDIPHENYLSILYLOXYMETHYL)-2-(DIETHYLOXYPHOSPHINOYL)-1,3-OXATHIOLANE

HRID 481708Notes

Reaction equation

HRID 481708 reaction equation
[CH2:1](OC(OCC)OCC)C.[Si:11]([O:28][CH2:29][CH:30]([OH:33])[CH2:31][SH:32])([C:24]([CH3:27])([CH3:26])[CH3:25])([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[P:34]([O:41][CH2:42][CH3:43])([O:38][CH2:39][CH3:40])[O:35]CC.P(Cl)(Cl)Cl>C1(C)C=CC=CC=1.ClCCl.[Cl-].[Zn+2].[Cl-].C1(C)C=CC(S(O)(=O)=O)=CC=1>[Si:11]([O:28][CH2:29][C@@H:30]1[O:33][C@@H:1]([P:34]([O:41][CH2:42][CH3:43])([O:38][CH2:39][CH3:40])=[O:35])[S:32][CH2:31]1)([C:24]([CH3:27])([CH3:25])[CH3:26])([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

9

Reactant 4

HCID 24387Phosphorus trichlorideHCID 31214Ethyl orthoformateHCID 31215Triethyl phosphiteHCID 212558771-t-BUTYLDIPHENYLSILYLOXY-3-MERCAPTO-2-PROPANOL

Product 1

HCID 131720781TRANS 5-(t-BUTYLDIPHENYLSILYLOXYMETHYL)-2-(DIETHYLOXYPHOSPHINOYL)-1,3-OXATHIOLANEYield 101.6%

Reagents, catalysts & solvents 4

HCID 6101p-Toluenesulfonic acidCatalystHCID 3007855ZincchlorideCatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of triethylorthoformate (0.64 g, 4.33 mmol), 1-t-butyldiphenylsilyloxy-3-mercapto-2-propanol (example 24) (5.00 g, 46.23 mmol) and p-toluenesulfonic acid (20 mg) in toluene (60 mL) was heated to reflux for 2h. The solvent was removed under reduced pressure to give a yellow oil. The oil was dissolved in dichloromethane (20.mL), zinc chloride (20 mg) was added along with triethyl phosphite (0.32 g, 1.93 mmol) at 0° C., followed by the addition of phosphorous trichloride (0.13 g, 0.95 mmol). After stirring at room temperature for 18h the solvent was removed under reduced pressure to give a colourless oil. The crude material was purified by flash chromatography with a mixture of hexanes and ethyl acetate (50:50) to give the compound as a colourless oil (0.97 g) in 67% yield as a mixture of cis and trans isomers (1:3.5). 1H NMR (300MHz, CDCl3) d: 1.03 (s, 9H, t-butyl), 1.32 (t, 6H, J=7.0Hz, CH3), 3.02 (m, 1H, H-4a), 3.18 and 3.24 (2dd, 1H, J=10.0 Hz, 6.0 Hz, H-4b), 3.72 (m, 2H, CH2OSi), 4.20 (m, 4H, CH2 CH3), 4.64 (p, 1H, J=6 Hz, H-5), 5.25 and 5.27 (2d, 1H, 2 JHP =9 Hz, H-2), 7.38 and 7.63 (m, 10H, Ar-H).

Workup

  1. temperatureto reflux for 2h
  2. customThe solvent was removed under reduced pressure
  3. customto give a yellow oil
  4. customwas removed under reduced pressure
  5. customto give a colourless oil
  6. customThe crude material was purified by flash chromatography with a mixture of hexanes and ethyl acetate (50:50)

Sources & evidence

ORD record
ord-0fefe1b30fe542a4bea3f3656ed2b04b
Source dataset
uspto-grants-1998_08
Patent number
US05789394

Reaction notes

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