Trimethylphosphine → HCID 131734125, compound

HRID 716179Notes

Reaction equation

HRID 716179 reaction equation
N([C:4]1[CH:5]=[N:6][S:7][C:8]=1[N:9]1[CH2:14][CH2:13][CH2:12][C@H:11]([NH:15][C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[CH2:10]1)=C=S.[N:23](C1C=NSC=1N1CCC[C@H](NC(=O)OC(C)(C)C)C1)=[N+]=[N-].[P:45]([CH3:48])([CH3:47])[CH3:46]>C1COCC1>[CH3:46][P:45](=[N:23][C:5]1[CH:4]=[C:8]([N:9]2[CH2:14][CH2:13][CH2:12][C@H:11]([NH:15][C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[CH2:10]2)[S:7][N:6]=1)([CH3:48])[CH3:47]

Participants

5

Reactant 3

HCID 68983TrimethylphosphineHCID 89183088HCID 89183088, compoundHCID 131734126HCID 131734126, compound

Product 1

HCID 131734125HCID 131734125, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

tert-butyl ((3S)-1-(4-isothiocyanato-5-isothiazolyl)-3-piperidinyl)carbamate. A dry, 25 mL pear flask was charged with tert-butyl ((3S)-1-(4-azido-5-isothiazolyl)-3-piperidinyl)carbamate (213 mg, 0.66 mmol), a stirbar, and dry THF (4 mL). The flask was fitted with a septa/Ar inlet and immersed into a ice-water bath. The solution was stirred for 10 min and a 1.0 M solution of PMe3 in THF (0.69 mL, 0.69 mmol) was added dropwise. The solution was stirred cold for 15 min. The solution was taken up into a 5 mL syringe (total volume=4.4 mL) to afford (S)-tert-butyl (1-(3-((trimethylphosphoranylidene)amino)isothiazol-5-yl)piperidin-3-yl)carbamate. A dry, 25 mL pear flask was charged with dry THF (2 mL), carbon disulfide (0.79 mL, 13.11 mmol), and a stirbar. The flask was fitted with a septa/Ar inlet/PTFE addition needle and immersed into an ice-water bath. The solution was stirred for 15 min. The syringe containing (S)-tert-butyl (1-(3-((trimethylphosphoranylidene)amino)isothiazol-5-yl)piperidin-3-yl)carbamate, as described above, was fitted to the PTFE addition needle. The solution was added via syringe pump over a 1 h period. The solution was stirred for 1 h, and concentrated in vacuo. The residue was dried in a vacuum oven (60° C., <1 mm Hg) for 1 h to afford tert-butyl ((3S)-1-(4-isothiocyanato-5-isothiazolyl) -3-piperidinyl)carbamate. The material was used without characterization.

Workup

  1. customThe flask was fitted with a septa/Ar inlet
  2. customimmersed into a ice-water bath
  3. stirringThe solution was stirred cold for 15 min
  4. customThe solution was taken up into a 5 mL syringe

Sources & evidence

ORD record
ord-b52a1750e342441aa4efd82b632f1a8a
Source dataset
uspto-grants-2015_11
Patent number
US09187486B2

Reaction notes

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