Water → Ethyl 6'-bromo-4-methoxy-1'-(2-(trimethylsilyl)ethylsulfonamido)-1',3'-dihydrospiro[cyclohexane-1,2'-indene]-1'-carboxylate

HRID 473014Notes

Reaction equation

HRID 473014 reaction equation
[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7]3([CH2:30][CH2:29][CH:28]([O:31][CH3:32])[CH2:27][CH2:26]3)[C:8]2([NH:16][S:17]([CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])(=[O:19])=[O:18])[C:11]([O:13][CH2:14][CH3:15])=C)=[CH:4][CH:3]=1.[OH2:33]>CCOC(C)=O>[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7]3([CH2:30][CH2:29][CH:28]([O:31][CH3:32])[CH2:27][CH2:26]3)[C:8]2([NH:16][S:17]([CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])(=[O:18])=[O:19])[C:11]([O:13][CH2:14][CH3:15])=[O:33])=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 962WaterHCID 67043662N-(6'-bromo-1'-(1-ethoxyvinyl)-4-methoxy-1',3'-dihydrospiro[cyclohexane-1,2'-indene]-1'-yl)-2-(trimethylsilyl)ethanesulfonamide

Product 1

HCID 67043624Ethyl 6'-bromo-4-methoxy-1'-(2-(trimethylsilyl)ethylsulfonamido)-1',3'-dihydrospiro[cyclohexane-1,2'-indene]-1'-carboxylateYield 50%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of NaIO4 (5.9503 g, 27.82 mmol) in water (40 mL) was added RuCl3 hydrate (0.0526 g, 0.25 mmol) followed by a solution of crude N-(6′-bromo-1′-(1-ethoxyvinyl)-4-methoxy-1′,3′-dihydrospiro[cyclohexane-1,2′-indene]-1′-yl)-2-(trimethylsilyl)ethanesulfonamide (9) (1.0894 g), obtained as described above, in EtOAc (60 mL). The resulting mixture was vigorously stirred at room temperature for 30 min and LC-MS indicated the disappearance of starting material. The organic layer was separated and the aqueous layer was extracted twice with EtOAc. The combined organic layers was dried over Na2SO4, filtered and evaporated. The residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate to afford ethyl 6′-bromo-4-methoxy-1′-(2-(trimethylsilyl)ethylsulfonamido)-1′,3′-dihydrospiro[cyclohexane-1,2′-indene]-1′-carboxylate (10) (0.5329 g, 50% in two steps). LC-MS tR=2.27 min in 3 min chromatography, m/z 568, 570 (MNa+), 333, 335; 1H NMR (400 MHz, CDCl3) δ 7.90 (s, 1H), 7.41 (d, J=7.9 Hz, 1H), 7.12 (d, J=8.2 Hz, 1H), 4.41-4.25 (m, 2H), 3.32 (s, 3H), 3.08-3.02 (m, 2H), 2.80 (d, J=15.8 Hz, 1H), 2.16-2.04 (m, 3H), 1.91-1.87 (m, 2H), 1.80-1.72 (m, 1H), 1.40-1.22 (m, 7H), 0.95-0.88 (m, 1H), 0.80-0.72 (m, 1H), 0.65-0.57 (m, 1H), −0.17 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 170.13, 142.21, 140.91, 132.97, 132.25, 126.52, 119.45, 78.49, 75.10, 61.87, 55.79, 53.06, 50.92, 38.15, 28.64, 28.38, 28.33, 27.82, 14.18, 9.98, −2.28.

Workup

  1. customobtained
  2. customThe organic layer was separated
  3. extractionthe aqueous layer was extracted twice with EtOAc
  4. dry with materialThe combined organic layers was dried over Na2SO4
  5. filtrationfiltered
  6. customevaporated
  7. customThe residue was purified by chromatography on silica gel
  8. washeluted with hexanes/ethyl acetate

Sources & evidence

ORD record
ord-2380c0c51a724e66b293a6a2ebf17c5c
Source dataset
uspto-grants-2014_01
Patent number
US08633212B2

Reaction notes

Loading…