Mercuric cyanide → [(2R,3R,4S,5S)-3,4-Dibenzoyloxy-5-cyanooxolan-2-yl]methyl benzoate

HRID 544733Notes

Reaction equation

HRID 544733 reaction equation
[C:1]([O:9][C@@H:10]1[C@H:14]([O:15][C:16](=[O:23])[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:13]([CH2:24][O:25][C:26](=[O:33])[C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[O:12][CH:11]1Br)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Hg](C#N)[C:36]#[N:37]>C(Cl)Cl>[C:1]([O:9][C@@H:10]1[C@H:14]([O:15][C:16](=[O:23])[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@@H:13]([CH2:24][O:25][C:26](=[O:33])[C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[O:12][C@H:11]1[C:36]#[N:37])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 11591Mercuric cyanideHCID 12736014HCID 12736014, compound

Product 1

HCID 2728914[(2R,3R,4S,5S)-3,4-Dibenzoyloxy-5-cyanooxolan-2-yl]methyl benzoateYield 524.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A suspension of 2,3,5-tri-O-benzoyl-D-ribofuranosyl bromide (I) (1.98 mol) and dry Hg(CN)2 (750 g; 2.97 mol) (mercury (II) cyanide was dried in vacuo at 140° for 12 hours) in dry CH2Cl2 (10.0 L), was stirred for 16 h at room temperature protected from moisture. The insolubles were collected and discarded. The filtrate was washed in succession with 5% aqueous KI (2×6.0 L) and water (2×6.0 L), dried over Na2SO4 (1.0 kg) and charcoal (35 g), then concentrated in vacuo to an oil. This material was diluted with EtOH (2.0 L) then concentrated in vacuo to an oil. The oil was slowly added to petroleum ether (bp, 63°-75°)-EtOH (21.0 L; 7.0 L) with vigorous stirring. The oil slowly solidified, and after 3 h of stirring, the resulting solid was collected and washed with petroleum ether (bp, 63°-75°) (1.0 L). This material was washed by resuspension (17 h) in EtOH (1.50 L). The off-white colored solid was collected, washed with petroleum ether (bp, 63°-75°) (2×500 ml) then dried to constant weight in vacuo to give 598 g (64°) of product; mp, 77.5°-79°. Additional reactions were carried out to give a total of 4894 g of product suitable for further transformation.

Workup

  1. customThe insolubles were collected
  2. washThe filtrate was washed in succession with 5% aqueous KI (2×6.0 L) and water (2×6.0 L)
  3. dry with materialdried over Na2SO4 (1.0 kg) and charcoal (35 g)
  4. concentrationconcentrated in vacuo to an oil
  5. additionThis material was diluted with EtOH (2.0 L)
  6. concentrationthen concentrated in vacuo to an oil
  7. additionThe oil was slowly added to petroleum ether (bp, 63°-75°)-EtOH (21.0 L; 7.0 L) with vigorous stirring
  8. stirringafter 3 h of stirring
  9. customthe resulting solid was collected
  10. washwashed with petroleum ether (bp, 63°-75°) (1.0 L)
  11. washThis material was washed by resuspension (17 h) in EtOH (1.50 L)
  12. customThe off-white colored solid was collected
  13. washwashed with petroleum ether (bp, 63°-75°) (2×500 ml)
  14. customthen dried to constant weight in vacuo
  15. customto give 598 g (64°) of product
  16. custommp, 77.5°-79°

Sources & evidence

ORD record
ord-75ed8fff392647e6b8b73bad6cefca70
Source dataset
uspto-grants-1984_05
Patent number
US04451648

Reaction notes

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