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Pyridine → (3aR,4S,6R,6aS)-6-{4-chloro-7H-pyrrolo[2,3-d]pyrimidin-7-yl}-2,2-dimethyl-hexahydrocyclopenta[d][1,3]dioxole-4-carbaldehyde

HRID 1054529
Notes
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Reaction equation

HRID 1054529 reaction equation
CCN=C=NCCCN(C)C.Cl.[Cl:13][C:14]1[C:15]2[CH:22]=[CH:21][N:20]([C@H:23]3[C@@H:27]4[O:28][C:29]([CH3:32])([CH3:31])[O:30][C@@H:26]4[C@@H:25]([CH2:33][OH:34])[CH2:24]3)[C:16]=2[N:17]=[CH:18][N:19]=1.N1C=CC=CC=1.C(O)(C(F)(F)F)=O>CS(C)=O.CCOC(C)=O>[Cl:13][C:14]1[C:15]2[CH:22]=[CH:21][N:20]([C@H:23]3[C@@H:27]4[O:28][C:29]([CH3:31])([CH3:32])[O:30][C@@H:26]4[C@@H:25]([CH:33]=[O:34])[CH2:24]3)[C:16]=2[N:17]=[CH:18][N:19]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 4

HCID 1049PyridineHCID 6422Trifluoroacetic acidHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochloride2×HCID 76844447((3aR,4R,6R,6aS)-6-(4-chloro-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl)methanol

Product 1

HCID 86705747
(3aR,4S,6R,6aS)-6-{4-chloro-7H-pyrrolo[2,3-d]pyrimidin-7-yl}-2,2-dimethyl-hexahydrocyclopenta[d][1,3]dioxole-4-carbaldehyde

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 8857Ethyl AcetateSolvent

Procedure

EDC.HCl (1.17 g, 6.11 mmol) was added to a solution of [(3aR,4R,6R,6aS)-6-{4-chloro-7H-pyrrolo[2,3-d]pyrimidin-7-yl}-2,2-dimethylhexahydrocyclopenta[d][1,3]dioxol-4-yl]methanol (0.66 g, 2.04 mmol) in anhydrous DMSO (11 ml) and stirred at RT. Pyridine (0.33 ml, 4.08 mmol) followed by TFA (0.15 ml, 2.04 mmol) were added to the reaction mixture and stirred at RT (the reaction mixture becomes a slightly yellow solution). The reaction monitored by LCMS. The reaction mixture becomes dark brown after 30 mins. After 1.5 hrs, a further aliquot of EDC.HCl (583 mg, 3.06 mmol) was added and allowed to stir for a further 1.5 hrs at RT. The reaction mixture was diluted with EtOAc (50 ml). This was washed with brine (2×50 ml), dried over Na2SO4 and evaporated in vacuo. The crude product was absorbed onto silica gel (3 ml) placed onto a silica column and purified eluting with EtOAc/heptanes (4/6) to yield a colorless oil (260 mg 40%); MS (ESI+) for C15H16ClN3O3 m/z 1 [M+H]+, 321.90; HPLC purity>95% (ret. time, 1.72 min). 1H NMR (250 MHz, CHLOROFORM-d) δ ppm 1.28-1.46 (3H, m), 1.54-1.77 (3H, m), 2.27-2.97 (2H, m), 3.17 (1H, td, J=8.72, 4.34 Hz), 4.82-5.13 (2H, m), 5.13-5.39 (1H, m), 6.45-6.84 (1H, m), 7.03-7.26 (1H, m), 8.47-8.86 (1H, m), 9.86 (1H, s).

Workup

  1. additionwere added to the reaction mixture
  2. stirringstirred at RT (the reaction mixture
  3. waitAfter 1.5 hrs
  4. stirringto stir for a further 1.5 hrs at RT
  5. washThis was washed with brine (2×50 ml)
  6. dry with materialdried over Na2SO4
  7. customevaporated in vacuo
  8. customThe crude product was absorbed onto silica gel (3 ml)
  9. custompurified
  10. washeluting with EtOAc/heptanes (4/6)
  11. customto yield a colorless oil (260 mg 40%)
  12. customHPLC purity>95% (ret. time, 1.72 min)

Sources & evidence

ORD record
ord-0a1a19a9eb1a4a31a1bfecac8ed09cda
Source dataset
uspto-grants-2016_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09394310B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes