Imidazole → (1R*,2R*)-Malonic acid (1-tert-butyldimethylsiloxy-1,2-dihydronaphthalen-2-yl) ester ethyl ester

HRID 28793Notes

Reaction equation

HRID 28793 reaction equation
[OH:1][C@@H:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[CH:4][C@H:3]1[O:12][C:13](=[O:20])[CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16].N1C=CN=C1.[Si:26](Cl)([C:29]([CH3:32])([CH3:31])[CH3:30])([CH3:28])[CH3:27]>ClCCl.CN(C1C=CC=CN=1)C>[CH2:18]([O:17][C:15](=[O:16])[CH2:14][C:13]([O:12][C@@H:3]1[CH:4]=[CH:5][C:6]2[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=2)[C@H:2]1[O:1][Si:26]([C:29]([CH3:32])([CH3:31])[CH3:30])([CH3:28])[CH3:27])=[O:20])[CH3:19]

Participants

6

Reactant 3

HCID 795ImidazoleHCID 28928tert-Butyldimethylsilyl chlorideHCID 9838469HCID 9838469, compound

Product 1

HCID 9843406(1R*,2R*)-Malonic acid (1-tert-butyldimethylsiloxy-1,2-dihydronaphthalen-2-yl) ester ethyl esterYield 90%

Reagents, catalysts & solvents 2

HCID 218852-DimethylaminopyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

To a dried round bottom flask, 7 (270 mg, 0.98 mmol), imidazole (134 mg, 1.96 mmol), dimethylaminopyridine (6 mg, 0.05 mmol) were dissolved in dichloromethane (4 mL). Tert-butyldimethylsilyl chloride (222 mg, 1.47 mmol) was then added portionwise and allowed to react for 24 hours. The reaction was then quenched with water, extracted with dichloromethane, dried over Na2SO4 and concentrated in vacuo. Flash chromatography (10% ethyl acetate in hexanes) gave a colourless oil 8 (343 mg, 90%). Rf 0.48 on silica gel (10% ethyl acetate:hexanes. IR (KBr, cm−1) 2983 (w), 1731 (s), 1453 (w), 1370 (m), 1150 (s), 1031 (m); 1H NMR (400 MHz, CDCl3) δ 7.41-7.39 (1H, m), 7.24-7.22 (2H, m), 7.07-7.05 (1H, m), 6.47 (1H, dd, J=9.9, 1.8 Hz), 5.83 (1H, dd, J=9.7, 2.7 Hz), 5.60 (1H, ddd, J=9.3, 2.9, 2.0 Hz), 5.00 (1H, dd, J=9.3, 0.5 Hz), 4.22-4.15 (2H, m), 3.40 (2H, dd, J=19.6, 16.0 Hz), 1.57 (1H, s), 1.25 (3H, t, J=7.1 Hz), 0.92 (9H, s), 0.13 (3H, s), 0.09 (3H, s); 13C NMR (400 MHz, CDCl3) δ 166.3, 166.2, 136.2, 132.1, 129.4, 128.0, 127.9, 126.5, 125.9, 125.7, 76.4, 71.6, 61.6, 41.7, 25.8, 18.1, 14.0, −4.3, −4.5. HRMS calcd for C17H21O5Si (M+-C4H9): 333.1158. Found: 333.1149.

Workup

  1. customto react for 24 hours
  2. customThe reaction was then quenched with water
  3. extractionextracted with dichloromethane
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-fb48294c9799412abe44e9cfd3bbfaf2
Source dataset
uspto-grants-2008_09
Patent number
US07420003B2

Reaction notes

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