Cyclohexene → HCID 54355047, compound

HRID 1086263Notes

Reaction equation

HRID 1086263 reaction equation
[C:1]([O:9][CH:10]([CH:15]1[CH:20]([O:21][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[CH:19]([O:29][CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[CH:18]([O:37][CH2:38][C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[CH:17]([CH2:45][O:46][CH2:47][C:48]2[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=2)[N:16]1[CH2:54]C1C=CC=CC=1)[CH2:11][CH2:12]CO)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1CCCCC=1>CO.[OH-].[OH-].[Pd+2]>[C:1]([O:9][CH:10]1[CH:15]2[N:16]([CH:17]([CH2:45][O:46][CH2:47][C:48]3[CH:49]=[CH:50][CH:51]=[CH:52][CH:53]=3)[CH:18]([O:37][CH2:38][C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=3)[CH:19]([O:29][CH2:30][C:31]3[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=3)[CH:20]2[O:21][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[CH2:54][CH2:12][CH2:11]1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 8079CyclohexeneHCID 53840815HCID 53840815, compound

Product 1

HCID 54355047HCID 54355047, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolvent

Procedure

To a solution of Compound (XV) (0.60 g; 0.74 mmoles) and cyclohexene (5 mL) in methanol (30 mL), Pearlman's catalyst (0.2 g) was added under a nitrogen atmosphere. The suspension was stirred at room temperature for 18 hours, then the catalyst was filtered through Celite and washed with methanol (20 mL). The combined organic layer was evaporated under reduced pressure to yield a crude oil, which was purified via flash chromatography (silica gel; 1:1 as a clear colorless oil (0.34 g) and recovered Compound (XV) (0.10 g; 16% recovery). The N-debenzylated alcohol (0.34 g) was dissolved in pyridine (20 mL) and cooled to -10° C., then methanesulfonyl chloride (0.04 mL) was added, and reaction was continued for 96 hours. The solvent was evaporated under reduced pressure and saturated aqueous sodium bicarbonate solution was added to the residue. After extraction with ether (2×60 mL), the combined organic solution was dried over magnesium sulfate and the solvent evaporated under reduced pressure. The crude product was purified via flash chromatorgraphy (silica gel; 1:1 ethyl acetate:hexane) to yield Octahydro-7,8,9-tris (phenylmethoxy)-6-[(phenylmethoxy)methyl]-2H-quinolizin1-ol benzoate (ester) (XVI) (0.16 g; 50%) as a colorless oil. IR (film from CDCl3) 1718 cm-1 (C=0); MS(CI--CH4) 698 (MH+), 576 (MH+ -PhCO2H); 1H nmr (CDCl3) δ 1.2 (m, 1H), 1.6-1.9 (m, 2H), 2.2 (d, 1H), 2.8 (t, 1H), 3.3-3.4 (m, 2H), 3.5-3.7 (m, 3H), 3.8 (m, 1H), 4.1 (t, 1H), 4.3 (d, 1H), 4.4-4.7 (m, 7H), 4.9 (d, 1H), 5.5 (s, 1H), 7.0-7.4 (m, 22H), 7.5 (m, 1H), 8.1 (m, 2H).

Workup

  1. filtrationthe catalyst was filtered through Celite
  2. washwashed with methanol (20 mL)
  3. customThe combined organic layer was evaporated under reduced pressure
  4. customto yield a crude oil, which
  5. customwas purified via flash chromatography (silica gel
  6. custom1:1 as a clear colorless oil (0.34 g) and recovered Compound (XV) (0.10 g; 16% recovery)
  7. dissolutionThe N-debenzylated alcohol (0.34 g) was dissolved in pyridine (20 mL)
  8. temperaturecooled to -10° C.
  9. additionmethanesulfonyl chloride (0.04 mL) was added
  10. customreaction
  11. waitwas continued for 96 hours
  12. customThe solvent was evaporated under reduced pressure and saturated aqueous sodium bicarbonate solution
  13. additionwas added to the residue
  14. extractionAfter extraction with ether (2×60 mL)
  15. dry with materialthe combined organic solution was dried over magnesium sulfate
  16. customthe solvent evaporated under reduced pressure
  17. customThe crude product was purified via flash chromatorgraphy (silica gel; 1:1 ethyl acetate:hexane)

Sources & evidence

ORD record
ord-300ebb4ea01541d7b2ac77c11b1df547
Source dataset
uspto-grants-1991_07
Patent number
US05028614

Reaction notes

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