methyl (2Z)-2-[(benzyloxy)carbonyl]amino-3-[3-bromo-4-(1,1-dioxido-3-oxo-2-[2-(trimethylsilyl)ethoxy]methylisothiazolidin-5-yl)phenyl]acrylate → Methyl (2S)-2-[(benzyloxy)carbonyl]amino-3-[3-bromo-4-(1,1-dioxido-3-oxo-2-[2-(trimethylsilyl)ethoxy]methylisothiazolidin-5-yl)phenyl]propanoate

HRID 724687Notes

Reaction equation

HRID 724687 reaction equation
[CH2:1]([O:8][C:9]([NH:11]/[C:12](=[CH:17]\[C:18]1[CH:23]=[CH:22][C:21]([CH:24]2[S:28](=[O:30])(=[O:29])[N:27]([CH2:31][O:32][CH2:33][CH2:34][Si:35]([CH3:38])([CH3:37])[CH3:36])[C:26](=[O:39])[CH2:25]2)=[C:20]([Br:40])[CH:19]=1)/[C:13]([O:15][CH3:16])=[O:14])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>C(O)C.[B-](F)(F)(F)F.COC1C([P@](CC[P@](C2C=CC=CC=2)C2C(OC)=CC=CC=2)C2C=CC=CC=2)=CC=CC=1.C1CC=CCCC=C1.[Rh]>[CH2:1]([O:8][C:9]([NH:11][C@@H:12]([CH2:17][C:18]1[CH:23]=[CH:22][C:21]([CH:24]2[S:28](=[O:30])(=[O:29])[N:27]([CH2:31][O:32][CH2:33][CH2:34][Si:35]([CH3:38])([CH3:37])[CH3:36])[C:26](=[O:39])[CH2:25]2)=[C:20]([Br:40])[CH:19]=1)[C:13]([O:15][CH3:16])=[O:14])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 1

HCID 58746853methyl (2Z)-2-[(benzyloxy)carbonyl]amino-3-[3-bromo-4-(1,1-dioxido-3-oxo-2-[2-(trimethylsilyl)ethoxy]methylisothiazolidin-5-yl)phenyl]acrylate

Product 1

HCID 58746899Methyl (2S)-2-[(benzyloxy)carbonyl]amino-3-[3-bromo-4-(1,1-dioxido-3-oxo-2-[2-(trimethylsilyl)ethoxy]methylisothiazolidin-5-yl)phenyl]propanoateYield 91%

Reagents, catalysts & solvents 2

HCID 10930696(1Z,5Z)-cycloocta-1,5-diene;(R)-(2-methoxyphenyl)-[2-[(2-methoxyphenyl)-phenylphosphanyl]ethyl]-phenylphosphane;rhodium;tetrafluoroborateCatalystHCID 702EthanolSolvent

Procedure

A solution of methyl (2Z)-2-[(benzyloxy)carbonyl]amino-3-[3-bromo-4-(1,1-dioxido-3-oxo-2-[2-(trimethylsilyl)ethoxy]methylisothiazolidin-5-yl)phenyl]acrylate (0.24 g, 0.37 mmol) in ethanol (10 mL) was bubble with nitrogen. (R,R)-(−)-1,2-bis[(o-methoxyphenyl)(phenyl)phosphino]ethane (1,5-cyclooctadiene) rhodium (I) tetrafluroborate (3 mg, 0.004 mmol) was added to the reaction solution and nitrogen was bubble through. After five cycles of vacuum/H2, the reaction was processed at a H2 pressure of 50 psi at room temperature. After 18 h, the solvent was removed under reduced pressure and the residue was purified with silica gel chromatography (5%–50% ethyl acetate/hexanes) to afford product as a white solid (0.22 g, 91%). 1H NMR (400 MHz, CDCl3): δ 7.47 (dd, J=13.3, 1.4 Hz, 1H), 7.33 (m, 5H), 7.24 (m, 1H), 7.14 (m, 1H), 5.47 (m, 1H), 5.06 (m, 4H), 4.10 (m, 1H), 3.72 (s, 3H), 3.65 (t, J=8.0 Hz, 2H), 3.43 (dd, J=17.5, 8.2 Hz, 1H), 3.18 (m, 2H), 3.04 (dd, J=17.5, 6.4 Hz, 1H), 0.97 (dd, J=8.4, 7.2 Hz, 2H), 0.01 (s, 9H). LCMS found for C27H35BrN2O8SSiNa (M+Na)+: m/z=677, 679.

Workup

  1. customwas bubble through
  2. customwas processed at a H2 pressure of 50 psi at room temperature
  3. customthe solvent was removed under reduced pressure
  4. customthe residue was purified with silica gel chromatography (5%–50% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-9d93c6c6a14f4bbcb192deefe10724d2
Source dataset
uspto-grants-2006_11
Patent number
US07141596B2

Reaction notes

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