Phenylsilane → HCID 54589870, compound

HRID 2403654Notes

Reaction equation

HRID 2403654 reaction equation
[N:1]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])=[N:2][C:3]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])=[O:4].[C:17]1([SiH3])[CH:22]=[CH:21][CH:20]=[CH:19]C=1.C1C23CC12C3>CC(O)C.ClCCl.CCCCC.CC(C)(C)/C(/O)=C/C(C(C)(C)C)=O.CC(C)(C)/C(/O)=C/C(C(C)(C)C)=O.CC(C)(C)/C(/O)=C/C(C(C)(C)C)=O.[Mn]>[C:20]12([N:1]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[NH:2][C:3]([O:5][C:6]([CH3:7])([CH3:8])[CH3:9])=[O:4])[CH2:19][CH:22]([CH2:21]1)[CH2:17]2

Participants

8

Reactant 3

HCID 12752PhenylsilaneHCID 97268Di-tert-butyl azodicarboxylateHCID 142022[1.1.1]Propellane

Product 1

HCID 54589870HCID 54589870, compoundYield 93%

Reagents, catalysts & solvents 4

HCID 1145621814324-99-3CatalystHCID 3776IsopropanolSolventHCID 6344DichloromethaneSolventHCID 8003PentaneSolvent

Conditions

Temperature
-15 °C

Procedure

Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III) (281 mg, 0.460 mmol) was dissolved in 2-propanol (100 mL) in a 1 L 3-necked flask equipped with addition funnel, gas inlet, and thermometer. The solution was cooled to −15° C. under nitrogen. Di-tert-butyl azodicarboxylate (8.11 g, 34.5 mmol) and phenylsilane (2.9 mL, 23 mmol) were dissolved in dichloromethane (100 mL) and this resulting orange solution was added to the above cooled solution dropwise over 10 minutes, maintaining the internal temperature at approximately −10° C. A solution of [1.1.1]propellane (Journal of the American Chemical Society (2001), 123(15), 3484-3492) (50 mL, 23 mmol, 0.46 M in pentane) was added to the reaction mixture in one portion at −15° C. The reaction was stirred at −15° C. for 30 minutes. The cold bath was removed and the reaction was allowed to warm to room temperature and stir for 4 hours. The reaction was concentrated and purification by flash column chromatography (5-20% ethyl acetate/heptanes) gave the title compound (6.38 g, 93%) as a clear oil which solidified upon standing. −ESI (M−H) 297.4; 1H NMR (400 MHz, CDCl3, δ): 6.26 (br. s., 1H), 2.37 (s, 1H), 2.02 (s, 6H), 1.45 (s, 18H).

Workup

  1. customequipped with addition funnel, gas inlet
  2. additionthis resulting orange solution was added to the above cooled solution dropwise over 10 minutes
  3. temperaturemaintaining the internal temperature at approximately −10° C
  4. customThe cold bath was removed
  5. temperatureto warm to room temperature
  6. stirringstir for 4 hours
  7. concentrationThe reaction was concentrated
  8. custompurification by flash column chromatography (5-20% ethyl acetate/heptanes)

Sources & evidence

ORD record
ord-a7d23fe1668443da9816c1e7b2db0903
Source dataset
uspto-grants-2014_08
Patent number
US08802688B2

Reaction notes

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