Diethylamine → 2-[3-[(tert-Butyldiphenylsilyl)oxy]propynyl)-7,8,9,10-tetrahydrophenanthridine

HRID 1198803Notes

Reaction equation

HRID 1198803 reaction equation
FC(F)(F)S(O[C:7]1[CH:20]=[CH:19][C:18]2[C:9](=[C:10]3[C:15](=[CH:16][N:17]=2)[CH2:14][CH2:13][CH2:12][CH2:11]3)[CH:8]=1)(=O)=O.[Si:23]([O:40][CH2:41][C:42]#[CH:43])([C:36]([CH3:39])([CH3:38])[CH3:37])([C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.C(NCC)C>C(OCC)(=O)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Si:23]([O:40][CH2:41][C:42]#[C:43][C:7]1[CH:20]=[CH:19][C:18]2[C:9](=[C:10]3[C:15](=[CH:16][N:17]=2)[CH2:14][CH2:13][CH2:12][CH2:11]3)[CH:8]=1)([C:36]([CH3:37])([CH3:38])[CH3:39])([C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1)[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

Participants

7

Reactant 3

HCID 8021DiethylamineHCID 610226Silane, (1,1-dimethylethyl)diphenyl(2-propynyloxy)-2×HCID 156780692-[(Trifluoromethanesulfonyl)oxy]-7,8,9,10-tetrahydrophenanthridine

Product 1

HCID 156780702-[3-[(tert-Butyldiphenylsilyl)oxy]propynyl)-7,8,9,10-tetrahydrophenanthridineYield 97%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a mixture of Compound 277 (1.28 g, 3.86 mmol), 3-[(tert-butyldiphenylsilyl)oxy]propyne (Compound 278, 1.48 g, 5.02 mmol), and diethylamine (800 mL, 7.73 mmol) in dry degassed N,N-dimethylformamide (7.7 mL) was added copper (I) iodide (74 mg, 0.39 mmol) followed by bis(triphenylphosphine)palladium(II) chloride (135 mg, 0.19 mmol). After being stirred in the dark for 11 hours under argon, the mixture was diluted with ethyl acetate (50 mL) and washed with saturated aqueous sodium bicarbonate (20 mL×2) and brine (20 mL). The organic layer was dried (Na2SO4) and evaporated in vacuo, and the residue was purified by flash column chromatography (silica, 10 percent ethyl ether in dichloromethane) to give 1.78 g (97 percent) of Compound 279: Rf =0.39 (10 percent ethyl acetate in dichloromethane); IR (film) νmax 3048, 2932, 2857, 2227, 1589, 1568, 1502, 1428, 1370, 1112 cm-1 ; 1H NMR (500 MHz, CDCl3) δ 8.59 (s, 1 H, H6), 7.95 (d, J=8.6 Hz, 1 H, H4), 7.92 (d, J=1.5 Hz, 1 H, H1), 7.84-7.78 (m, 4 H, aromatic), 7.53 (dd, J=8.6, 1.5 Hz, 1 H, H3), 7.48-7.39 (m, 6 H, aromatic), 4.62 (s, 2 H, C≡CCH2O), 3.04 (t, J=5.8 Hz, 2 H, H10), 2.87 (t, J=5.8 Hz, 2 H, H7), 2.01-1.93 (m, 2 H, CH2), 1.93-1.85 (m, 2 H, CH2), 1.12 (s, 9 H, t-Bu); 13C NMR (125 MHz, CDCl3) δ 152.8, 145.6, 141.0, 135.6, 133.1, 130.6, 130.2, 129.7, 129.6, 127.6, 127.5, 127.2, 120.7, 88.4, 85.3, 53.2, 27.0, 26.7, 24.8, 22.2, 22.1, 19.2; MS (FAB+) m/e (rel intensity) 476 (M+H, 100), 418 (9), 388 (12), 220 (11), 197 (9); HRMS for C32H34NOSi (M+H), calcd 476.2410, found 476.2410.

Workup

  1. customin dry
  2. customdegassed N,N-dimethylformamide (7.7 mL)
  3. washwashed with saturated aqueous sodium bicarbonate (20 mL×2) and brine (20 mL)
  4. dry with materialThe organic layer was dried (Na2SO4)
  5. customevaporated in vacuo
  6. customthe residue was purified by flash column chromatography (silica, 10 percent ethyl ether in dichloromethane)

Sources & evidence

ORD record
ord-1bf3497978b64909b2e84a6332092004
Source dataset
uspto-grants-1994_01
Patent number
US05281710

Reaction notes

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