methyl 2-acetoxy-3-(7-methyl-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazol-5-yl)acrylate → (R)-Methyl 2-acetoxy-3-(7-methyl-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazol-5-yl)propanoate

HRID 501933Notes

Reaction equation

HRID 501933 reaction equation
[C:1]([O:4][C:5](=[CH:10][C:11]1[CH:19]=[C:18]([CH3:20])[C:17]2[C:13](=[CH:14][N:15]([CH2:21][O:22][CH2:23][CH2:24][Si:25]([CH3:28])([CH3:27])[CH3:26])[N:16]=2)[CH:12]=1)[C:6]([O:8][CH3:9])=[O:7])(=[O:3])[CH3:2]>[B-](F)(F)(F)F.CC[C@H]1P(C2C(P3[C@H](CC)CC[C@H]3CC)=CC=CC=2)[C@H](CC)CC1.C1[CH][CH]CC[CH][CH]C1.[Rh].ClCCl>[C:1]([O:4][C@H:5]([CH2:10][C:11]1[CH:19]=[C:18]([CH3:20])[C:17]2[C:13](=[CH:14][N:15]([CH2:21][O:22][CH2:23][CH2:24][Si:25]([CH3:28])([CH3:27])[CH3:26])[N:16]=2)[CH:12]=1)[C:6]([O:8][CH3:9])=[O:7])(=[O:3])[CH3:2]

Participants

4

Reactant 1

HCID 68460947methyl 2-acetoxy-3-(7-methyl-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazol-5-yl)acrylate

Product 1

HCID 59424274(R)-Methyl 2-acetoxy-3-(7-methyl-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazol-5-yl)propanoate

Reagents, catalysts & solvents 2

HCID 11549211CID 11549211CatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of methyl 2-acetoxy-3-(7-methyl-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazol-5-yl)acrylate (825 mg, 2.04 mmol) in degassed (by bubbling nitrogen) dichloromethane (20.00 mL) under nitrogen was added solid (−)-1,2-bis-((2R,5R)-2,5-diethylphospholano)benzene-(cyclooctadiene)rhodium(I) tetrafluoroborate (100.00 mg), all at once. The reaction was placed under a hydrogen atmosphere (55 psi), and shaken for 6 h. The reaction was concentrated and purified by column chromatography (25% ethyl acetate/hexanes) to give 700 mg (84%) as a colorless oil. 1H-NMR (CDCl3, 500 MHz) δ −0.03 (s, 9H), 0.94 (t, J=8.2, 2H), 2.07 (s, 3H), 2.61 (s, 3H), 3.11 (dd, J=14.3, 8.9, 1H), 3.20 (dd, J=14.3, 4.6, 1H), 3.64 (t, J=8.5, 2H), 3.72 (s, 3H), 5.26 (dd, J=8.5, 4.6, 1H), 5.72 (s, 2H), 6.93 (s, 1H), 7.33 (s, 1H), 8.02 (s, 1H).

Workup

  1. concentrationThe reaction was concentrated
  2. custompurified by column chromatography (25% ethyl acetate/hexanes)
  3. customto give 700 mg (84%) as a colorless oil

Sources & evidence

ORD record
ord-0752d103256b4d78aae9caee4adc0d7c
Source dataset
uspto-grants-2010_08
Patent number
US07772244B2

Reaction notes

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