Triacetoxyperiodinane → N-{[1,6-Diethyl-4-(tetrahydro-2H-pyran-4-ylamino)-1H-pyrazolo[3,4-b]pyridin-5-yl]methyl}-N'-({6-fluoro-3'-[(4-oxo-1-piperidinyl)methyl]-3-biphenylyl}methyl)-1,3-benzenedicarboxamide

HRID 564639Notes

Reaction equation

HRID 564639 reaction equation
[CH2:1]([N:3]1[C:7]2=[N:8][C:9]([CH2:54][CH3:55])=[C:10]([CH2:19][NH:20][C:21]([C:23]3[CH:28]=[CH:27][CH:26]=[C:25]([C:29]([NH:31][CH2:32][C:33]4[CH:34]=[C:35]([C:40]5[CH:45]=[CH:44][CH:43]=[C:42]([CH2:46][N:47]6[CH2:52][CH2:51][CH:50]([OH:53])[CH2:49][CH2:48]6)[CH:41]=5)[C:36]([F:39])=[CH:37][CH:38]=4)=[O:30])[CH:24]=3)=[O:22])[C:11]([NH:12][CH:13]3[CH2:18][CH2:17][O:16][CH2:15][CH2:14]3)=[C:6]2[CH:5]=[N:4]1)[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(Cl)Cl>[CH2:1]([N:3]1[C:7]2=[N:8][C:9]([CH2:54][CH3:55])=[C:10]([CH2:19][NH:20][C:21]([C:23]3[CH:28]=[CH:27][CH:26]=[C:25]([C:29]([NH:31][CH2:32][C:33]4[CH:34]=[C:35]([C:40]5[CH:45]=[CH:44][CH:43]=[C:42]([CH2:46][N:47]6[CH2:48][CH2:49][C:50](=[O:53])[CH2:51][CH2:52]6)[CH:41]=5)[C:36]([F:39])=[CH:37][CH:38]=4)=[O:30])[CH:24]=3)=[O:22])[C:11]([NH:12][CH:13]3[CH2:18][CH2:17][O:16][CH2:15][CH2:14]3)=[C:6]2[CH:5]=[N:4]1)[CH3:2]

Participants

4

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 44181305N-{[1,6-Diethyl-4-(tetrahydro-2H-pyran-4-ylamino)-1H-pyrazolo[3,4-b]pyridin-5-yl]methyl}-N'-({6-fluoro-3'-[(4-hydroxy-1-piperidinyl)methyl]-3-biphenylyl}methyl)-1,3-benzenedicarboxamide

Product 1

HCID 57813377N-{[1,6-Diethyl-4-(tetrahydro-2H-pyran-4-ylamino)-1H-pyrazolo[3,4-b]pyridin-5-yl]methyl}-N'-({6-fluoro-3'-[(4-oxo-1-piperidinyl)methyl]-3-biphenylyl}methyl)-1,3-benzenedicarboxamideYield 14.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of N-{[1,6-diethyl-4-(tetrahydro-2H-pyran-4-ylamino)-1H-pyrazolo[3,4-b]pyridin-5-yl]methyl}-N′-({6-fluoro-3′-[(4-hydroxy-1-piperidinyl)methyl]-3-biphenyl-yl}methyl)-1,3-benzenedicarboxamide (85 mg, 0.114 mmol) in DCM (0.5 mL) was added Dess-Martin Periodinane (0.417 mL, 0.125 mmol). This mixture was stirred at room temperature for 40 min. The reaction was quenched with Na2SO3 (˜0.2 mL, 5%), concentrated and purified using a Gilson HPLC (with 0.1% TFA). The product fraction was concentrated and basified with an amine cartridge to afford 0.0121 g (14%) of the title compound. LC-MS m/z 746 (M+H)+; 1H NMR (400 MHz, CD3OD) δ ppm 1.31 (t, J=7.40 Hz, 3 H) 1.41 (t, J=7.15 Hz, 3 H) 1.64-1.83 (m, 4 H) 1.99-2.02 (m, J=1.25 Hz, 1 H) 2.04-2.07 (m, 1 H) 2.38 (t, J=6.02 Hz, 2 H) 2.59-2.78 (m, 4 H) 3.00 (q, J=7.45 Hz, 2 H) 3.60 (t, J=11.29 Hz, 2 H) 3.65-3.69 (m, 1 H) 3.71-3.78 (m, 1 H) 3.93-4.02 (m, J=11.54 Hz, 2 H) 4.10-4.20 (m, 1 H) 4.41 (q, J=7.19 Hz, 2 H) 4.58 (s, 2 H) 4.69 (s, 2 H) 7.09-7.18 (m, 1 H) 7.31-7.50 (m, 5 H) 7.51-7.59 (m, 2 H) 7.95-8.03 (m, 3 H) 8.31 (s, 1 H).

Workup

  1. customThe reaction was quenched with Na2SO3 (˜0.2 mL, 5%)
  2. concentrationconcentrated
  3. custompurified
  4. concentrationThe product fraction was concentrated

Sources & evidence

ORD record
ord-e42ab109ac304d939c2249cbd8316dee
Source dataset
uspto-grants-2011_11
Patent number
US08067408B2

Reaction notes

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