Triphenylphosphine → HCID 68862586, compound

HRID 2099129Notes

Reaction equation

HRID 2099129 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([Li])CCC.Br[C:26]1[CH:27]=[C:28]2[C:33]3=[C:34]([CH2:36][CH2:37][CH2:38][N:32]3[CH:31]=[C:30]([C:39]([O:41][CH2:42][CH3:43])=[O:40])[C:29]2=[O:44])[CH:35]=1.[C:45]([O:49][C:50]([NH:52][CH2:53][C:54]#[CH:55])=[O:51])([CH3:48])([CH3:47])[CH3:46]>O1CCCC1.C(NCC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Cu](I)I>[C:45]([O:49][C:50]([NH:52][CH2:53][C:54]#[C:55][C:26]1[CH:27]=[C:28]2[C:33]3=[C:34]([CH2:36][CH2:37][CH2:38][N:32]3[CH:31]=[C:30]([C:39]([O:41][CH2:42][CH3:43])=[O:40])[C:29]2=[O:44])[CH:35]=1)=[O:51])([CH3:48])([CH3:47])[CH3:46]

Participants

9

Reactant 4

HCID 11776TriphenylphosphineHCID 11073648tert-butyl N-(prop-2-yn-1-yl)carbamateHCID 57720101HCID 57720101, compoundHCID 178418339Butyllithium

Product 1

HCID 68862586HCID 68862586, compound

Reagents, catalysts & solvents 4

HCID 83717Copper iodideCatalystHCID 167845palladium(II) acetateCatalystHCID 8021DiethylamineSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A yellow suspension of palladium acetate (73 mg, 0.32 mmol) and triphenylphosphine (191 mg, 0.72 mmol) in dry tetrahydrofuran (6 mL) under argon was cooled to 0° C. A solution of n-butyllithium (2.5M in hexanes, 284 uL) was added dropwise and after 15 minutes the dark green suspension is warmed to room temperature for 15 minutes. This suspension is then cannulated under argon into a white suspension of ethyl 9-bromo-1-oxo-6,7-dihydro-1H,5H-pyrido[3,2,1-ij]quinoline-2-carboxylate (337 mg, 1 mmol), copper iodide (84 mg, 0.44 mmol) and t-butoxycarbonylpropargylamine (198 mg, 1.28 mmol) in diethylamine (6 mL). The brown suspension is warmed to 45° C. for 2 hours then filtered off and preabsorbed on silica gel. Chromatography on silica gel eluting with 0-5% (9:1 MeOH/20 M NH3) in dichloromethane provided the title compound as a brown oil. ESMS m/z 411 (MH+). 1H NMR (CDCl3) δ 8.23(s, 1H), 8.12 (d, 1H), 7.29 (d, 1H), 5.1 (m, 1H), 4.35 (q, 2H), 4.15 (m, 2×2H), 2.97 (t, 2H), 2.19 (tt, 2H), 1.49 (s, 9H), 1.38 (t, 3H).

Workup

  1. temperatureis warmed to room temperature for 15 minutes
  2. temperatureThe brown suspension is warmed to 45° C. for 2 hours
  3. filtrationthen filtered off
  4. custompreabsorbed on silica gel

Sources & evidence

ORD record
ord-a496082827b24480947dc3bdba732607
Source dataset
uspto-grants-2009_08
Patent number
US07569550B2

Reaction notes

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