Triethylamine → (E)-ethyl 3-(1-Ethyl-1,3,4,9-tetrahydro-1-(2-hydroxyethyl)-8-isopropylpyrano[3,4-b]indol-6-yl)acrylate

HRID 268689Notes

Reaction equation

HRID 268689 reaction equation
CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.Br[C:24]1[CH:25]=[C:26]2[C:30](=[C:31]([CH:33]([CH3:35])[CH3:34])[CH:32]=1)[NH:29][C:28]1[C:36]([CH2:42][CH2:43][OH:44])([CH2:40][CH3:41])[O:37][CH2:38][CH2:39][C:27]2=1.C(N(CC)CC)C.[C:52]([O:56][CH2:57][CH3:58])(=[O:55])[CH:53]=[CH2:54]>C(#N)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH2:40]([C:36]1([CH2:42][CH2:43][OH:44])[C:28]2[NH:29][C:30]3[C:26]([C:27]=2[CH2:39][CH2:38][O:37]1)=[CH:25][C:24](/[CH:54]=[CH:53]/[C:52]([O:56][CH2:57][CH3:58])=[O:55])=[CH:32][C:31]=3[CH:33]([CH3:35])[CH3:34])[CH3:41]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 80271Tri-o-tolylphosphineHCID 111644512-(6-Bromo-1-ethyl-1,3,4,9-tetrahydro-8-isopropylpyrano[3,4-b]indol-1-yl)ethanol

Product 1

HCID 59639720(E)-ethyl 3-(1-Ethyl-1,3,4,9-tetrahydro-1-(2-hydroxyethyl)-8-isopropylpyrano[3,4-b]indol-6-yl)acrylateYield 56.9%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

A suspension of Pd(OAc)2 (0.2 g, 0.8 mmol), P(o-tolyl)3 (0.25 g, 0.8 mmol), 2-(6-bromo-1-ethyl-1,3,4,9-tetrahydro-8-isopropylpyrano[3,4-b]indol-1-yl)ethanol (1.5 g, 4.1 mmol), triethylamine (1.5 ml, 11 mmol), and ethyl acrylate (1.8 ml, 16 mmol) in acetonitrile (45 ml) and stirred under a nitrogen atmosphere at 100° C. for 24 hr. The mixture was allowed to cool, quenched with water, worked-up with dichloromethane, and washed with brine. The organic layers were dried over MgSO4 and concentrated under reduced pressure. The crude product was chromatographed on silica hexane/EtOAc (6:4) to give the product (0.9 g, 56%). %). 1H NMR (300 MHz, CDCl3) δ 8.07 (br, NH), 7.83 (d, 1H), 7.53 (d, 1H), 7.28 (d, 1H), 6.43 (d, 1H), 4.27 (m, 2H), 4.04 (m, 2H), 3.73 (m, 2H), 3.19 (m, 1H), 2.84 (m, 1H), 2.77 (d, 1H), 2.52 (br, 1H), 2.20 (m, 1H), 2.09 (m, 1H), 1.92 (m, 1H), 1.38 (d, 6H), 1.35 (t, 3H), 0.95 (t, 3H); ESI (+) MS m/e=386 (MH+), ESI (−) MS m/e=384 (MH−).

Workup

  1. temperatureto cool
  2. customquenched with water
  3. washwashed with brine
  4. dry with materialThe organic layers were dried over MgSO4
  5. concentrationconcentrated under reduced pressure
  6. customThe crude product was chromatographed on silica hexane/EtOAc (6:4)

Sources & evidence

ORD record
ord-ccc0f9ea9dde4294a8132eadcd602439
Source dataset
uspto-grants-2008_11
Patent number
US07446122B2

Reaction notes

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