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

HRID 2249565Notes

Reaction equation

HRID 2249565 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, 1), 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-929982d6f86f4eb4b2889fcd9a70deb9
Source dataset
uspto-grants-2008_01
Patent number
US07314886B2

Reaction notes

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