Iodine → 6-(Methylsulfanyl)-2,3-dihydro-1H-pyrrolizine-1-carbonitrile

HRID 65083Notes

Reaction equation

HRID 65083 reaction equation
II.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:22][S:23]([C:25]1[CH:26]=[C:27]2[CH:31]([C:32]#[N:33])[CH2:30][CH2:29][N:28]2[CH:34]=1)=O.[I-].[Na+].S([O-])([O-])(=O)=S.[Na+].[Na+]>C(#N)C.CCOCC>[CH3:22][S:23][C:25]1[CH:26]=[C:27]2[CH:31]([C:32]#[N:33])[CH2:30][CH2:29][N:28]2[CH:34]=1

Participants

8

Reactant 5

HCID 807Iodine3×HCID 5238Sodium IodideHCID 11776TriphenylphosphineHCID 24477Sodium ThiosulfateHCID 145709186-Methylsulfinyl-1,2-dihydro-3H-pyrrolo[1,2-a]pyrrole-1-carbonitrile

Product 1

HCID 145709196-(Methylsulfanyl)-2,3-dihydro-1H-pyrrolizine-1-carbonitrile

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolvent2×

Procedure

Powdered iodine (1 eq.) was added to a stirred solution of triphenylphosphine (1.15 eq.) in dry acetonitrile (10 ml/mmol of sulfoxide to be used) in a nitrogen atmosphere. The mixture was stirred until the iodine color was no longer present and a yellow colored suspension had formed. The sulfoxide (IX) (1 eq.) in dry acetonitrile (2.5 ml/mmol sulfoxide) was added in one portion. This was immediately followed by adding the solid powdered sodium iodide (2 eq.). The mixture was stirred and rapidly changed to a dark color. TLC showed that the reaction was complete after 1 min. After stirring for no more than 5 min. the solution was poured into a mixture of 5% sodium thiosulfate solution and ether. The mixture was shaken until the iodine color had disappeared, the ether phase was separated and washed with a 5% sodium bicarbonate solution. The ether solution was dried over sodium sulfate and evaporated in vacuo. The crude material was passed through a short column of silica gel (30 g/g of crude product) using dichloromethane. The excess triphenylphosphine came off with the solvent front and was followed almost immediately by the product compound (X). The sulfide (X) was obtained as an oil which was sufficiently pure to be used in the next step.

Workup

  1. customa yellow colored suspension had formed
  2. stirringAfter stirring for no more than 5 min. the solution
  3. customthe ether phase was separated
  4. washwashed with a 5% sodium bicarbonate solution
  5. dry with materialThe ether solution was dried over sodium sulfate
  6. customevaporated in vacuo

Sources & evidence

ORD record
ord-f9fa3b777eaa48358e9a0828720e3ac2
Source dataset
uspto-grants-1986_09
Patent number
US04612325

Reaction notes

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