Diisopropylethylamine → Ethyl 8-(phenylselanyl)-1,4-dioxaspiro[4.5]decane-8-carboxylate

HRID 1849832Notes

Reaction equation

HRID 1849832 reaction equation
C(N(C(C)C)CC)(C)C.C([Li])CCC.[O:15]1[C:19]2([CH2:24][CH2:23][CH:22]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:21][CH2:20]2)[O:18][CH2:17][CH2:16]1.[C:30]1([Se:36]Br)[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>O1CCCC1>[C:30]1([Se:36][C:22]2([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:23][CH2:24][C:19]3([O:18][CH2:17][CH2:16][O:15]3)[CH2:20][CH2:21]2)[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

Participants

6

Reactant 4

HCID 81531DiisopropylethylamineHCID 123446BromoselenobenzeneHCID 10488810Ethyl 1,4-dioxaspiro(4.5)decane-8-carboxylateHCID 178418339Butyllithium

Product 1

HCID 86703720Ethyl 8-(phenylselanyl)-1,4-dioxaspiro[4.5]decane-8-carboxylateYield 76.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of diisopropylethyl amine (5.59 g, 55.30 mmol) in anhydrous tetrahydrofuran (150 mL) was added a solution of butyllithium (1.6 M in hexanes, 34.5 mL, 55.30 mmol) at 0° C. The reaction solution was stirred at the same temperature for 1 hour, then added a solution of ethyl 1,4-dioxaspiro[4.5]decane-8-carboxylate (10.80 g, 50.00 mmol) in anhydrous tetrahydrofuran (20 mL) at −78° C. The reaction mixture was stirred at the same temperature for 1 h then added phenylselenium bromide (11.90 g, 50.70 mmol). The mixture was continued to stir at −78° C. for 5 hour, then at ambient temperature for 16 hour. The reaction was quenched with saturated sodium hydrogencarbonate (200 mL), diluted with ethyl acetate (200 mL), saturated ammonium chloride (3×150 mL), brine (3×100 mL), dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to dryness. The residue was purified by column chromatography with ethyl acetate in hexanes (10%) to afford the title compound as a viscous liquid (14.10 g, 76%): 1H NMR (300 MHz, CDCl3) δ 7.54 (d, J=7.6 Hz, 1H), 7.37-7.32 (m, 1H), 7.26 (dd, J=7.0, 7.0 Hz, 2H), 4.05 (dd, J=7.1 Hz, 2H), 3.90 (d, J=3.4 Hz, 4H), 2.20-2.12 (m, 2H), 2.00-1.88 (m, 2H), 1.82-1.70 (m, 2H), 1.57-1.46 (m, 2H), 1.14 (t, J=7.1 Hz, 3H).

Workup

  1. stirringThe reaction mixture was stirred at the same temperature for 1 h
  2. stirringto stir at −78° C. for 5 hour
  3. waitat ambient temperature for 16 hour
  4. customThe reaction was quenched with saturated sodium hydrogencarbonate (200 mL)
  5. additiondiluted with ethyl acetate (200 mL), saturated ammonium chloride (3×150 mL), brine (3×100 mL)
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated in vacuo to dryness
  9. customThe residue was purified by column chromatography with ethyl acetate in hexanes (10%)

Sources & evidence

ORD record
ord-6fe7624c571a4a5cad546ce3abf9c22c
Source dataset
uspto-grants-2015_02
Patent number
US08952169B2

Reaction notes

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