Diethylamine → N-[(Phenyloxy)carbonyl)-6a,10a-epoxy-10-oxo-3-(trimethylacetoxy)-6-[6-trimethylsilyl-3(Z)-hexene-1,5-diynyl]-5,6,6a,7,8,9,10,10a-octahydrophenanthridine

HRID 260394Notes

Reaction equation

HRID 260394 reaction equation
Cl[CH:2]=[CH:3][C:4]#[C:5][Si:6]([CH3:9])([CH3:8])[CH3:7].C(NCC)C.[C:15]1([O:21][C:22]([N:24]2[CH:37]([C:38]#[CH:39])[C:36]34[O:40][C:31]3([C:32](=[O:41])[CH2:33][CH2:34][CH2:35]4)[C:30]3[CH:29]=[CH:28][C:27]([O:42][C:43](=[O:48])[C:44]([CH3:47])([CH3:46])[CH3:45])=[CH:26][C:25]2=3)=[O:23])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>C1C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[C:15]1([O:21][C:22]([N:24]2[CH:37]([C:38]#[C:39]/[CH:2]=[CH:3]\[C:4]#[C:5][Si:6]([CH3:9])([CH3:8])[CH3:7])[C:36]34[O:40][C:31]3([C:32](=[O:41])[CH2:33][CH2:34][CH2:35]4)[C:30]3[CH:29]=[CH:28][C:27]([O:42][C:43](=[O:48])[C:44]([CH3:46])([CH3:45])[CH3:47])=[CH:26][C:25]2=3)=[O:23])[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1

Participants

7

Reactant 3

HCID 8021DiethylamineHCID 53822143(4-Chlorobut-3-en-1-yn-1-yl)(trimethyl)silaneHCID 86747475N-[(Phenyloxy)carbonyl]-6a, 10a-epoxy-6-ethynyl-10-oxo-3-(trime-thylacetoxy)-5,6,6a, 7,8,9,10,10a-octahydrophenanthridine

Product 1

HCID 86747474N-[(Phenyloxy)carbonyl)-6a,10a-epoxy-10-oxo-3-(trimethylacetoxy)-6-[6-trimethylsilyl-3(Z)-hexene-1,5-diynyl]-5,6,6a,7,8,9,10,10a-octahydrophenanthridineYield 32%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 241BenzeneSolvent2×

Conditions

Temperature
25 °C

Procedure

A mixture of Pd(PPh3)4 (185 mg, 0.16 mmol), 1-chloro-4-(trimethylsilyl)-but-1-en-3-yne (0.776 g, 4.89 mmol), and diethylamine (0.51 mL, 4.93 mmol) in degassed benzene (5 mL) was stirred at 25° C. for 15 minutes. The resultant solution was added to a mixture of Compound 230 (1.50 g, 3.26 mmol) and CuI (124 mg, 0.65 mmol) in degassed benzene (15 mL) via a syringe followed by stirring at 25° C. for one hour. The reaction mixture was quenched by saturated aqueous NH4Cl, extracted with ethyl ether (80 mL), washed with brine, dried over anhydrous Na2SO4, and concentrated in vacuo. Purification of the residue by flash column chromatography (silica gel, 25 percent ethyl ether in petroleum ether) provided a solid product Compound 231 (0.606 g, 32 percent): Rf =0.43 (silica, 50 percent ethyl ether in petroleum ether); IR (CHCl3) νmax 2964, 1721, 1494, 1378, 1305, 1270, 1253, 1202, 1181, 1122, 846 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 8.40 (d, J=8.7 Hz, 1 H, H1), 7.44-7.10 (m, 6 H, H4 and aromatic), 6.99 (dd, J=8.7, 2.4 Hz, 1 H, H2), 5.98 (d, J=1.5 Hz, 1 H, H6), 5.84 (d, J=11.1 Hz, 1 H, olefinic), 5.69 (br d, J=11.1 Hz, 1 H, olefinic), 2.81-2.66 (m, 2 H, H9), 2.41-2.26 (m, 2 H, H7), 2.10-1.86 (m, 2 H, H8), 1.33 (s, 9 H, COC(CH3)3), 0.22 (s, 9 H, SiC(CH3)3); MS (FAB+) m/e (rel intensity) 582 (M+H, 100), 525 (13), 460 (48), 406 (8), 360 (6), 320 (8), 279 (25), 246 (5);HRMS for C34H36NO6Si (M+H), calcd 582.2312, found 582.2322.

Workup

  1. stirringby stirring at 25° C. for one hour
  2. customThe reaction mixture was quenched by saturated aqueous NH4Cl
  3. extractionextracted with ethyl ether (80 mL)
  4. washwashed with brine
  5. dry with materialdried over anhydrous Na2SO4
  6. concentrationconcentrated in vacuo
  7. customPurification of the residue by flash column chromatography (silica gel, 25 percent ethyl ether in petroleum ether)

Sources & evidence

ORD record
ord-038a55c51a0d4a8e84486102226c8a0f
Source dataset
uspto-grants-1996_06
Patent number
US05527805

Reaction notes

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