Bromide ion → [3,5-Bis-methoxymethoxy-4-((E)-3-phenyl-allyl)-benzyloxy]-tert-butyl-dimethyl-silane

HRID 1177218Notes

Reaction equation

HRID 1177218 reaction equation
[H-].[Na+].[CH3:3][O:4][CH2:5][O:6][C:7]1[CH:8]=[C:9]([CH:19]=[C:20]([O:22][CH2:23][O:24][CH3:25])[CH:21]=1)[CH2:10][O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13].CN([CH2:29][CH2:30]N(C)C)C.[Li][CH2:35][CH2:36][CH2:37][CH3:38].[Br-].[CH2:40]1[CH2:44]OC[CH2:41]1>[Cu]I>[CH3:3][O:4][CH2:5][O:6][C:7]1[CH:8]=[C:9]([CH:19]=[C:20]([O:22][CH2:23][O:24][CH3:25])[C:21]=1[CH2:44]/[CH:40]=[CH:41]/[C:30]1[CH:29]=[CH:38][CH:37]=[CH:36][CH:35]=1)[CH2:10][O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13]

Participants

8

Reactant 6

HCID 259Bromide ionHCID 8028TetrahydrofuranHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 24758Sodium hydrideHCID 99975163,5-Bis(methoxymethoxy)benzyl tert-butyldimethylsilyl etherHCID 178418339Butyllithium

Product 1

HCID 66755605[3,5-Bis-methoxymethoxy-4-((E)-3-phenyl-allyl)-benzyloxy]-tert-butyl-dimethyl-silaneYield 34%

Reagents, catalysts & solvents 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst

Conditions

Temperature
0 °C

Procedure

To a suspension of NaH (60%, 18 g, 0.45 mol) in THF (2 L) were added (3,5-bis-methoxymethoxy-benzyloxy)-tert-butyl-dimethyl-silane (220c) (100 g, 0.3 mol) and TMEDA (81.6 g, 0.6 mol) in one portion. The mixture was stirred at 0° C. for 1 hr. n-BuLi (2.5 M in hexane, 180 mL, 0.45 mol) was added drop wise to the mixture at −20° C. and the solution was stirred for 1 hr. CuI (114 g, 0.6 mol) was added in one portion and the reaction was stirred at −20° C. for another 1 hr. Then the mixture was added drop wise cinamy bromide (65 g, 0.3 mol) at −20° C. After stirring for another 30 min, TLC (EtOAc/petroleum ether=1/10) showed that the reaction was complete. The reaction mixture was quenched with H2O (500 mL). The organic layer was separated and the aqueous layer was extracted with EtOAc (2×500 mL). The organic layers were combined, washed with brine (1 L), dried over Na2SO4 and concentrated to give a dark oil. The crude oil was purified by column chromatography (EtOAc/petroleum ether=1/10) to give the title compound (55 g, 34%) as a yellow liquid. 1H NMR (400 MHz, CDCl3): δ 7.16-7.41 (m, 5H), 6.82 (s, 2H), 6.47 (m, 2H), 5.22 (s, 4H), 4.71 (s, 2H), 3.62 (d, 2H), 3.45 (s, 6H), 0.94 (s, 9H), 0.12 (s, 6H).

Workup

  1. stirringthe solution was stirred for 1 hr
  2. stirringthe reaction was stirred at −20° C. for another 1 hr
  3. stirringAfter stirring for another 30 min
  4. customThe reaction mixture was quenched with H2O (500 mL)
  5. customThe organic layer was separated
  6. extractionthe aqueous layer was extracted with EtOAc (2×500 mL)
  7. washwashed with brine (1 L)
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated
  10. customto give a dark oil
  11. customThe crude oil was purified by column chromatography (EtOAc/petroleum ether=1/10)

Sources & evidence

ORD record
ord-5bcb7e2768f74ff082870b986367a432
Source dataset
uspto-grants-2010_11
Patent number
US07842713B2

Reaction notes

Loading…