Triacetoxyperiodinane → tert-butyl benzyl(4-(5-chloro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine-4-carbonyl)-bicyclo[2.2.2]octan-1-yl)carbamate

HRID 1969868Notes

Reaction equation

HRID 1969868 reaction equation
[CH2:1]([N:8]([C:16]12[CH2:23][CH2:22][C:19]([CH:24]([C:26]3[C:31]([Cl:32])=[CH:30][N:29]=[C:28]4[N:33]([Si:36]([CH:43]([CH3:45])[CH3:44])([CH:40]([CH3:42])[CH3:41])[CH:37]([CH3:39])[CH3:38])[CH:34]=[CH:35][C:27]=34)[OH:25])([CH2:20][CH2:21]1)[CH2:18][CH2:17]2)[C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(Cl)Cl>[CH2:1]([N:8]([C:16]12[CH2:23][CH2:22][C:19]([C:24]([C:26]3[C:27]4[CH:35]=[CH:34][N:33]([Si:36]([CH:43]([CH3:45])[CH3:44])([CH:37]([CH3:39])[CH3:38])[CH:40]([CH3:41])[CH3:42])[C:28]=4[N:29]=[CH:30][C:31]=3[Cl:32])=[O:25])([CH2:20][CH2:21]1)[CH2:18][CH2:17]2)[C:9](=[O:15])[O:10][C:11]([CH3:13])([CH3:14])[CH3:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 58557653tert-butyl benzyl(4-((5-chloro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridin-4-yl)(hydroxy)methyl)bicyclo[2.2.2]octan-1-yl)carbamate

Product 1

HCID 58557141tert-butyl benzyl(4-(5-chloro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine-4-carbonyl)-bicyclo[2.2.2]octan-1-yl)carbamateYield 77%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of tert-butyl benzyl(4-((5-chloro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridin-4-yl)(hydroxy)methyl)bicyclo[2.2.2]octan-1-yl)carbamate (1.26 g, 1.93 mmol) in DCM (10 mL) was added Dess-Martin periodinane (1.64 g, 3.86 mmol). The reaction was stirred at ambient temperature for about 3 h and was diluted with DCM (10 mL). The mixture was washed with saturated aqueous NaHCO3 (2×15 mL), brine (15 mL), dried over anhydrous MgSO4, filtered, and concd under reduced pressure. The resulting oil was purified by silica gel chromatography eluting with a gradient of 0-25% EtOAc in heptane to give tert-butyl benzyl(4-(5-chloro-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine-4-carbonyl)-bicyclo[2.2.2]octan-1-yl)carbamate (0.965 g, 77%) as a yellow oil: 1H NMR (400 MHz, CDCl3) δ 8.15 (s, 1H), 7.32-7.24 (m, 3H), 7.23-7.08 (m, 3H), 6.23 (d, J=3.5, 1H), 4.53 (s, 2H), 2.13-2.03 (m, 6H), 1.95-1.83 (m, 6H), 1.81-1.74 (m, 3H), 1.41 (s, 9H), 1.12-1.06 (m, 18H).

Workup

  1. washThe mixture was washed with saturated aqueous NaHCO3 (2×15 mL), brine (15 mL)
  2. dry with materialdried over anhydrous MgSO4
  3. filtrationfiltered
  4. customThe resulting oil was purified by silica gel chromatography
  5. washeluting with a gradient of 0-25% EtOAc in heptane

Sources & evidence

ORD record
ord-f74b758a71ff4abdba211ef63cd9f799
Source dataset
uspto-grants-2013_04
Patent number
US08426411B2

Reaction notes

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