Ethyl acetate hexane → HCID 57546164, compound

HRID 913946Notes

Reaction equation

HRID 913946 reaction equation
[Cl:1][C:2]1[CH:10]=[C:9]([C:11]([O:13][CH2:14][C:15]2([C:28]3[CH:33]=[CH:32][C:31]([F:34])=[CH:30][CH:29]=3)[CH2:20][CH2:19][N:18]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:17][CH2:16]2)=[CH2:12])[C:8]2[C:4](=[CH:5][N:6]([CH2:35][O:36][CH2:37][CH2:38][Si:39]([CH3:42])([CH3:41])[CH3:40])[N:7]=2)[CH:3]=1.C(OCC)(=O)C.CCCCCC>ClC(Cl)C.CC1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)=CC=1.CC(O)=O.CC(O)=O.[Ru]>[Cl:1][C:2]1[CH:10]=[C:9]([C@H:11]([O:13][CH2:14][C:15]2([C:28]3[CH:33]=[CH:32][C:31]([F:34])=[CH:30][CH:29]=3)[CH2:20][CH2:19][N:18]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:17][CH2:16]2)[CH3:12])[C:8]2[C:4](=[CH:5][N:6]([CH2:35][O:36][CH2:37][CH2:38][Si:39]([CH3:42])([CH3:40])[CH3:41])[N:7]=2)[CH:3]=1

Participants

5

Reactant 2

HCID 21226206Ethyl acetate hexane2×HCID 57546023HCID 57546023, compound

Product 1

HCID 57546164HCID 57546164, compound

Reagents, catalysts & solvents 2

HCID 11007467Diacetato[(S)-(-)-2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl]ruthenium(II)CatalystHCID 63651,1-DichloroethaneSolvent

Procedure

tert-Butyl 4-((1-(5-chloro-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazol-7-yl)vinyloxy)methyl)-4-(4-fluorophenyl)piperidine-1-carboxylate (1 g, 1.62 mmol) was transferred to a parr bottle (pre-purged with nitrogen) and dissolved in dichloroethane (40 mL). The resulting solution was purged by bubbling nitrogen through it for 45 min. To the bottle was quickly added diacetato[(S)-(−)-2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl]ruthenium(II) (233 mg, 0.259 mmol). The bottle was purged for 10 additional min, and quickly affixed to the parr shaker. After 3 vaccuum/pressurize cycles, the shaker was pressurized to 65 psi and shaken overnight. The crude reaction mixture was loaded onto a pre-conditioned column of 12% ethyl acetate/n-hexane. After several volumes, the polarity was increased to 25% ethyl acetate/n-hexane to give 850 mg (85%) as a viscous amber oil. 1H-NMR (CDCl3, 500 MHz) δ 8.00 (s, 1H), 7.48 (d, J=1.8 Hz, 1H), 7.31 (dd, J=8.5, 5.2 Hz, 2H), 7.03 (dd, J=8.9, 8.6 Hz, 2H), 6.77 (s, 1H), 5.67 (d, J=10.7 Hz, 1H), 5.64 (d, J=10.7 Hz, 1H), 4.93 (q, J=6.4 Hz, 1H), 3.72 (m, 2H), 3.59 (t, J=8.4 Hz, 2H), 3.37 (d, J=9.2 Hz, 1H), 3.34 (d, J=9.2 Hz, 1H), 3.05 (m, 2H), 2.19 (m, 1H), 2.08 (m, 1H), 1.94 (m, 1H), 1.87 (m, 1H), 1.44 (s, 9H), 1.43 (d, J=6.4 Hz, 3H), 0.91 (dd, J=9.2, 7.3 Hz, 2H), −0.06 (s, 9H); 13C NMR (126 MHz, CDCl3) δ ppm 161.5 (d, J=245 Hz), 155.1, 145.6, 138.9, 135.8, 128.9 (d, J=7.7 Hz), 128.3, 122.82, 122.76, 122.2, 117.6, 115.2 (d, J=21 Hz), 81.9, 79.4, 77.9, 73.9, 67.6, 41.3, 40.3, 32.3, 32.0, 28.6, 22.8, 17.9, −1.4. Mass spec.: 618.39 (MH)+.

Workup

  1. customThe resulting solution was purged
  2. customby bubbling nitrogen through it for 45 min
  3. customThe bottle was purged for 10 additional min
  4. customThe crude reaction mixture
  5. customto give 850 mg (85%) as a viscous amber oil

Sources & evidence

ORD record
ord-9c3d0689324c4ca88a282f6cb0a1bfca
Source dataset
uspto-grants-2011_09
Patent number
US08026257B2

Reaction notes

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