Tributylstannane → 4-Methoxy-6-methoxycarbonyl-10-phenylmethyl-6,7,8,9-tetrahydropyrido[1,2-a]indole

HRID 567378Notes

Reaction equation

HRID 567378 reaction equation
C([SnH](CCCC)CCCC)CCC.N(C(C)(C)C#N)=NC(C)(C)C#N.[CH3:26][O:27][C:28]1[CH:29]=[CH:30][CH:31]=[C:32]2[C:36]=1[N:35]1[CH:37]([C:41]([O:43][CH3:44])=[O:42])[CH2:38][CH2:39][CH2:40][CH:34]1[CH:33]2[CH2:45][C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1.C1(CC2C3C(=C(OC)C=CC=3)N(C(CCC)C(OC)=O)C=2)C=CC=CC=1>C1(C)C=CC=CC=1.O1CCOCC1>[CH3:26][O:27][C:28]1[CH:29]=[CH:30][CH:31]=[C:32]2[C:36]=1[N:35]1[CH:37]([C:41]([O:43][CH3:44])=[O:42])[CH2:38][CH2:39][CH2:40][C:34]1=[C:33]2[CH2:45][C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1

Participants

7

Reactant 4

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 22740584Methyl 2-[3-phenylmethyl-7-methoxyindol-1-yl]pentanoateHCID 22741322HCID 22741322, compound

Product 1

HCID 99029604-Methoxy-6-methoxycarbonyl-10-phenylmethyl-6,7,8,9-tetrahydropyrido[1,2-a]indole

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 312751,4-DioxaneSolvent

Procedure

A solution of 1.8 gm (4.7 mmol) of the product from Part B and 4 mL (15 mmol) of tri-n-butyltin hydride in 5.0 mL of toluene was heated to reflux and treated dropwise with a solution of 85 mg (0.5 mmol) of 2,2′-azobis(2-methylpropionitrile). The solution was refluxed 1 hour after the addition, cooled, evaporated in vacuo, taken up in ethyl acetate, shaken with aqueous potassium floride, and filtered. The organic phase was washed with saturated sodium chloride, dried over sodium sulfate, and evaporated in vacuo to give a mixture of 4-methoxy-6-methoxycarbonyl-10-phenylmethyl-6,7,8,9,9a,10-hexahydropyrido[1,2-a]indole and methyl 2-[3-phenylmethyl-7-methoxyindol-1-yl]pentanoate which was dissolved in 25 mL of dioxane and stirred with 450 mg (2 mmol) of dichlorodicyanoquinone for 30 minutes. The solution was evaporated in vacuo, taken up in dichloromethane, filtered through florisil, and evaporated in vacuo. The residue was chromatographed on silica gel eluting with a gradient hexane/10-20% ethyl ether to give the title compound, 75 mg, 5%, as an amorphous solid. 1H NMR (CDCl3) δ: 1.70 (m, 1H), 1.85 (m, 1H), 2.20 (m, 1H), 2.35 (m, 1H), 2.70 (m, 1H), 3.00 (m, 1H), 3.70 (s, 3H), 3.80 (s, 3H), 4.00 (q, 2H), 5.65 (m, 1H), 6.50 (d, 1H), 6.90 (t, 1H), 7.00 (d, 1H), 7.10 (m, 1H), 7.20 (m, 4H).

Workup

  1. temperatureto reflux
  2. temperatureThe solution was refluxed 1 hour
  3. additionafter the addition
  4. temperaturecooled
  5. customevaporated in vacuo
  6. filtrationfiltered
  7. washThe organic phase was washed with saturated sodium chloride
  8. dry with materialdried over sodium sulfate
  9. customevaporated in vacuo
  10. customto give
  11. customThe solution was evaporated in vacuo
  12. filtrationfiltered through florisil
  13. customevaporated in vacuo
  14. customThe residue was chromatographed on silica gel eluting with a gradient hexane/10-20% ethyl ether

Sources & evidence

ORD record
ord-38ceaf75057a4f4e98bc92dc277755e5
Source dataset
uspto-grants-2001_01
Patent number
US06177440B1

Reaction notes

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