Pyridine → C-(3-aminophenyl)-N-[2-(tert-butyldiphenylsilanyloxy)-ethyl]methanesulfonamide

HRID 1259040Notes

Reaction equation

HRID 1259040 reaction equation
C([Si](C1C=CC=CC=1)(C1C=CC=CC=1)OCCN)(C)(C)C.N1C=CC=CC=1.[N+](C1C=C(CS(Cl)(=O)=O)C=CC=1)([O-])=O.[C:42]([Si:46]([C:70]1[CH:75]=[CH:74][CH:73]=[CH:72][CH:71]=1)([C:64]1[CH:69]=[CH:68][CH:67]=[CH:66][CH:65]=1)[O:47][CH2:48][CH2:49][NH:50][S:51]([CH2:54][C:55]1[CH:60]=[CH:59][CH:58]=[C:57]([N+:61]([O-])=O)[CH:56]=1)(=[O:53])=[O:52])([CH3:45])([CH3:44])[CH3:43]>ClCCl.CO.[Pd]>[NH2:61][C:57]1[CH:56]=[C:55]([CH2:54][S:51]([NH:50][CH2:49][CH2:48][O:47][Si:46]([C:42]([CH3:45])([CH3:44])[CH3:43])([C:70]2[CH:75]=[CH:74][CH:73]=[CH:72][CH:71]=2)[C:64]2[CH:65]=[CH:66][CH:67]=[CH:68][CH:69]=2)(=[O:52])=[O:53])[CH:60]=[CH:59][CH:58]=1

Participants

8

Reactant 4

HCID 1049PyridineHCID 110010432-(t-Butyldiphenylsilyloxy)ethylamineHCID 13196775(3-Nitrophenyl)methanesulfonyl chlorideHCID 66688970N-[2-(tert-butyldiphenyl-silanyloxy)-ethyl]-C-(3-nitrophenyl)-methanesulfonamide

Product 1

HCID 66690163C-(3-aminophenyl)-N-[2-(tert-butyldiphenylsilanyloxy)-ethyl]methanesulfonamide

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of 2-(tert-butyldiphenyl-silanyloxy)-ethylamine (0.76 g, 2.54 mmol) in dichloromethane (15 ml) and pyridine (0.21 ml, 2.54 mmol) at room temperature was added 3-nitro-alpha-toluenesulfonyl chloride (0.50 g, 2.12 mmol) in one portion and the reaction stirred overnight. The reaction was diluted with dichloromethane (35 ml), washed with aqueous copper sulfate and brine, dried over sodium sulfate and concentrated to give a crude product. The crude N-[2-(tert-butyldiphenyl-silanyloxy)-ethyl]-C-(3-nitrophenyl)-methanesulfonamide (theoretical 1.06 g, 2.13 mmol) was dissolved in methanol (30 ml) and placed under an atmosphere of nitrogen prior to the addition of 10% Pd/C (10 Wt %, 100 mg) in one portion. The reaction mixture was evacuated, placed under an atmosphere of hydrogen (1 bar) and stirred vigorously overnight. The reaction was filtered through celite and the filtrate was concentrated in vacuo to afford the crude reduced product. The crude C-(3-aminophenyl)-N-[2-(tert-butyldiphenylsilanyloxy)-ethyl]methanesulfonamide obtained above (theoretical 0.996 g) was dissolved in tetrahydrofuran (20 ml) and a 1M solution of tetrabutlyammonium fluoride in tetrahydrofuran (2.34 ml, 2.34 mmol) was added in one portion. The reaction was stirred at room temperature for 2 h then diluted with ethyl acetate (30 ml) and brine (30 ml), the organic layer was dried over sodium sulfate, filtered and concentrated in vacuo. The crude mixture was purified by column chromatography using dichloromethane:methanol as eluent to give the named product (0.411 g, 84% over 3 steps); Rf (DCM:MeOH 95:5) 0.06; LCMS Rt=0.83 min, m/z (ES−) 229 (M−H).

Workup

  1. washwashed with aqueous copper sulfate and brine
  2. dry with materialdried over sodium sulfate
  3. concentrationconcentrated
  4. customto give a crude product
  5. customThe reaction mixture was evacuated
  6. stirringstirred vigorously overnight
  7. filtrationThe reaction was filtered through celite
  8. concentrationthe filtrate was concentrated in vacuo
  9. customto afford the crude reduced product

Sources & evidence

ORD record
ord-e8fd6f25af224e20acc876155864de3f
Source dataset
uspto-grants-2013_06
Patent number
US08466201B2

Reaction notes

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