Water → 5-(2-(1,3-dioxolan-2-yl)vinyl)-N-cyclohexyl-1-tosyl-1H-pyrrolo[2,3-b]pyridin-4-amine

HRID 1969862Notes

Reaction equation

HRID 1969862 reaction equation
[Br-].[O:2]1[CH2:6][CH2:5][O:4][CH:3]1[CH2:7][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[CH3:27]C(C)([O-])C.[K+].[CH:33]1([NH:39][C:40]2[C:45](C=O)=[CH:44][N:43]=[C:42]3[N:48]([S:51]([C:54]4[CH:60]=[CH:59][C:57]([CH3:58])=[CH:56][CH:55]=4)(=[O:53])=[O:52])[CH:49]=[CH:50][C:41]=23)[CH2:38][CH2:37][CH2:36][CH2:35][CH2:34]1.O>C1COCC1>[O:4]1[CH2:5][CH2:6][O:2][CH:3]1[CH:7]=[CH:27][C:45]1[CH:44]=[N:43][C:42]2[N:48]([S:51]([C:54]3[CH:60]=[CH:59][C:57]([CH3:58])=[CH:56][CH:55]=3)(=[O:52])=[O:53])[CH:49]=[CH:50][C:41]=2[C:40]=1[NH:39][CH:33]1[CH2:34][CH2:35][CH2:36][CH2:37][CH2:38]1

Participants

6

Reactant 4

HCID 962WaterHCID 2724194(1,3-Dioxolan-2-ylmethyl)triphenylphosphonium bromideHCID 23665647Potassium tert-butoxideHCID 585572344-(cyclohexylamino)-1-tosyl-1H-pyrrolo[2,3-b]pyridine-5-carbaldehyde

Product 1

HCID 672172225-(2-(1,3-dioxolan-2-yl)vinyl)-N-cyclohexyl-1-tosyl-1H-pyrrolo[2,3-b]pyridin-4-amineYield 67%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

An oven dried flask under nitrogen was charged with ((1,3-dioxolan-2-yl)methyl)triphenylphosphonium bromide (2.23 g, 5.19 mmol) and THF (14 mL). The flask was cooled to about 0° C. in an ice bath and potassium tert-butoxide (0.591 g, 5.00 mmol) was added. The mixture was stirred for about 30 min at about 0° C. and a solution of 4-(cyclohexylamino)-1-tosyl-1H-pyrrolo[2,3-b]pyridine-5-carbaldehyde (0.750 g, 1.89 mmol) in THF (4 mL) was added dropwise over about 10 min. The reaction was allowed to warm to ambient temperature and stirred for about 16 h. Water (10 mL) was added and the reaction mixture was extracted with Et2O (3×10 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered, and concd under reduced pressure. The crude oil was purified by silica gel chromatography eluting 0-50% EtOAc in DCM to give 5-(2-(1,3-dioxolan-2-yl)vinyl)-N-cyclohexyl-1-tosyl-1H-pyrrolo[2,3-b]pyridin-4-amine (0.590 g, 67%) as a mixture of E and Z isomers: LC/MS (Table 1, Method c) Rt=1.69 min, 1.73 min; MS m/z: 468 (M+H)+, 468 (M+H)+.

Workup

  1. customAn oven dried flask under nitrogen
  2. temperatureto warm to ambient temperature
  3. stirringstirred for about 16 h
  4. extractionthe reaction mixture was extracted with Et2O (3×10 mL)
  5. dry with materialThe combined organic extracts were dried over anhydrous Na2SO4
  6. filtrationfiltered
  7. customThe crude oil was purified by silica gel chromatography
  8. washeluting 0-50% EtOAc in DCM

Sources & evidence

ORD record
ord-06e09d078fe64a20876cc32de3ad0c20
Source dataset
uspto-grants-2013_04
Patent number
US08426411B2

Reaction notes

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