Potassium Cyanide → N-[(Phenyloxy)carbonyl]-6-[3(Z)-hexene-1,5-diynyl]-6a,10a-epoxy-2-methoxy-10-oxo-5,6,6a,7,8,9,10,10a,-octahydrophenanthridine

HRID 260405Notes

Reaction equation

HRID 260405 reaction equation
[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[C:25]/[CH:26]=[CH:27]\[C:28]#[C:29][Si](C)(C)C)[C:22]34[O:34][C:17]3([C:18](=[O:35])[CH2:19][CH2:20][CH2:21]4)[C:16]3[CH:15]=[C:14]([O:36][CH3:37])[CH:13]=[CH:12][C:11]2=3)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C-]#N.[K+]>O.CCO.C1COCC1.[N+]([O-])([O-])=O.[Ag+]>[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[C:25]/[CH:26]=[CH:27]\[C:28]#[CH:29])[C:22]34[O:34][C:17]3([C:18](=[O:35])[CH2:19][CH2:20][CH2:21]4)[C:16]3[CH:15]=[C:14]([O:36][CH3:37])[CH:13]=[CH:12][C:11]2=3)=[O:9])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 2

HCID 9032Potassium CyanideHCID 86747542N-[(Phenyloxy)carbonyl)-6-[6-(trimethylsilyl)-3(Z)-hexene-1,5-diynyl]-6a,10a-epoxy-2-methoxy-10-oxo-5,6,6a,7,8,9,10,10a-octahydrophenanthridine

Product 1

HCID 88413792N-[(Phenyloxy)carbonyl]-6-[3(Z)-hexene-1,5-diynyl]-6a,10a-epoxy-2-methoxy-10-oxo-5,6,6a,7,8,9,10,10a,-octahydrophenanthridineYield 88%

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 18504229Ethanol tetrahydrofuran waterSolvent

Procedure

Silver nitrate (1.43 g, 8.44 mmol) was added to a solution of Compound 315 (1.08 g, 2.11 mmol) in 48 mL of H2O-EtOH-THF (1:1:1) at 25° C. followed by stirring for 15 minutes. Potassium cyanide (0.962 g, 14.8 mmol) was then added and the mixture was stirred for one hour, concentrated in vacuo to 20 mL, poured into saturated aqueous sodium bicarbonate (30 mL), and extracted with dichloromethane (3×40 mL). The combined organic layers were dried (MgSO4) and evaporated in vacuo, and the residue was purified by flash column chromatography (silica, 35 percent ethyl ether in petroleum ether) to give 0.807 g (88 percent) of Compound 316: white foam Rf =0.22 (silica, 40 percent ethyl ether in petroleum ether); IR (CHCl3) νmax 3299, 2947, 1716, 1609, 1590, 1501, 1493, 1380, 1299, 1253 cm-1 ; 1H NMR (500 MHz, CDCl3 ) 7.96 (d, J=2.9 Hz, 1 H, aromatic), 7.38-7.07 (m, 6 H, aromatic), 6.89 (dd, J=8.9, 2.9 Hz, 1 H, aromatic), 5.88 (s, 1 H, H6), 5.77 and 5.74 (ABq, J=11.2 Hz, 2 H, olefinic), 3.81 (s, 3 H, OCH3), 3.16 (d, J=1.5 Hz, 1 H, C≡CH), 2.74 (dt, J=15.3, 5.0 Hz, 1 H, H9), 2.67 (ddd, J=15.3, 10.1, 6.1 Hz, 1 H, H9), 2.36-2.26 (m, 2 H, H7), 1.99-1.89 (m, 2 H, H8); 13C NMR (125 MHz, CDCl3) δ 201.5, 157.2, 154.1, 151.0, 129.3, 128.7, 128.5, 125.7, 124.1, 121.4, 120.4, 120.3, 114.8, 114.7, 90.6, 85.1, 82.7, 80.3, 74.9, 57.4, 55.5, 48.3, 38.8, 23.8, 18.6; MS (FAB+) m/e (rel intensity) 439 (M+, 100), 364 (8), 176 (19), 120 (10); HRMS for C27H21NO5 (M+), calcd 439.1420, found 439.1434.

Workup

  1. stirringthe mixture was stirred for one hour
  2. concentrationconcentrated in vacuo to 20 mL
  3. additionpoured into saturated aqueous sodium bicarbonate (30 mL)
  4. extractionextracted with dichloromethane (3×40 mL)
  5. dry with materialThe combined organic layers were dried (MgSO4)
  6. customevaporated in vacuo
  7. customthe residue was purified by flash column chromatography (silica, 35 percent ethyl ether in petroleum ether)

Sources & evidence

ORD record
ord-066367dfec5a4db08065f0ccdb4d0a8f
Source dataset
uspto-grants-1996_06
Patent number
US05527805

Reaction notes

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