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Phosphorus trichloride → trans-4-(t-Butyldimethylsilyloxymethyl)-2-(diethyloxyphosphinoyl)-1,3-dithiolane

HRID 636872
Notes
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Reaction equation

HRID 636872 reaction equation
[Si:1]([O:8][CH2:9][CH:10]1[CH2:14][S:13][CH:12](OCC)[S:11]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH2:18]([O:20][P:21]([O:25]CC)[O:22][CH2:23][CH3:24])[CH3:19].P(Cl)(Cl)Cl>ClCCl.[Cl-].[Zn+2].[Cl-]>[Si:1]([O:8][CH2:9][C@@H:10]1[CH2:14][S:13][C@@H:12]([P:21]([O:22][CH2:23][CH3:24])([O:20][CH2:18][CH3:19])=[O:25])[S:11]1)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:2])[CH3:3]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 24387Phosphorus trichlorideHCID 31215Triethyl phosphiteHCID 212558444-t-Butyldimethylsilyloxymethyl-2-ethoxy-1,3-dithiolane

Product 1

HCID 131720785trans-4-(t-Butyldimethylsilyloxymethyl)-2-(diethyloxyphosphinoyl)-1,3-dithiolaneYield 46%

Reagents, catalysts & solvents 2

HCID 3007855Zincchloride
Catalyst
HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 4-(t-butyldimethylsilyloxymethyl)-2-ethoxy-1,3-dithiolane (example 48) (37.1 g, 126 mmol) and triethylphosphite (14.3 mL, 83.0 mmol, 0.66 eq) in dichloromethane (100 mL) were added phosphorus trichloride (3.6 mL, 42.0 mmol, 0.33 eq) and zinc chloride (catalytic) at 0° c. The solution was stirred at 0° C. for 2 hr and at room temperature for 18 hr. The solvent was evaporated and the crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (80:20 to 60:40) to give 3.64 g of the cis isomer, 8.62 g of the trans isomer and 9.95 g of the mixture (2:1 trans:cis) for a total yield of 46%.

Workup

  1. customThe solvent was evaporated
  2. customthe crude material was purified by flash chromatography with a mixture of hexane and ethyl acetate (80:20 to 60:40)

Sources & evidence

ORD record
ord-d41354932f1c4f70bb5c97aac7d44b98
Source dataset
uspto-grants-2001_02
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06194576B1

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes