tert-Butyl methyl ether → 3-Nitro-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-1-(t-butyldimethylsilyloxy)-2-hydroxybenzene

HRID 218272Notes

Reaction equation

HRID 218272 reaction equation
C([Li])CCC.[Br-].[CH3:7][O:8][C:9]1[CH:10]=[C:11]([CH:32]=[C:33]([O:37][CH3:38])[C:34]=1[O:35][CH3:36])[CH2:12][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Si:39]([O:46][C:47]1[C:54]([O:55][Si](C(C)(C)C)(C)C)=[C:53]([N+:63]([O-:65])=[O:64])[CH:52]=[CH:51][C:48]=1[CH:49]=O)([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40].C(OC)(C)(C)C>CCCCCC.C1COCC1.O>[N+:63]([C:53]1[C:54]([OH:55])=[C:47]([O:46][Si:39]([C:42]([CH3:44])([CH3:43])[CH3:45])([CH3:40])[CH3:41])[C:48](/[CH:49]=[CH:12]\[C:11]2[CH:32]=[C:33]([O:37][CH3:38])[C:34]([O:35][CH3:36])=[C:9]([O:8][CH3:7])[CH:10]=2)=[CH:51][CH:52]=1)([O-:65])=[O:64]

Participants

8

Reactant 4

HCID 15413tert-Butyl methyl etherHCID 370917Triphenyl(3,4,5-trimethoxybenzyl)phosphonium bromideHCID 85996491HCID 85996491, compoundHCID 178418339Butyllithium

Product 1

HCID 601306873-Nitro-6-[(Z)-2-(3,4,5-trimethoxyphenyl)vinyl]-1-(t-butyldimethylsilyloxy)-2-hydroxybenzeneYield 36.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-20 °C

Procedure

n-Butyllithium (1.6 mL of a 1.6 M solution in hexane, 2.6 mmol) was added dropwise to a suspension of 3,4,5-trimethoxybenzyltriphenylphosphonium bromide (1.1 g, 2.1 mmol) in THF (15 mL) at −20° C. The brick red solution was stirred at −20° C. for 30 min, cooled to −78° C., then a solution of 45 (0.88 g, 2.14 mmol) in THF (5 mL) was added dropwise. The reaction mixture was allowed to warm to rt overnight, then poured into t-BuOMe (ca. 20 mL) and water (ca. 20 mL), the layers were separated and the aqueous layer was re-extracted with t-BuOMe. The combined organic extracts were washed with brine, dried (Na2SO4) and evaporated to dryness. Purification by column chromatography (SiO2, EtOAc:cyclohexane 1:1) gave 46 (0.355 g, 29%):

Workup

  1. temperaturecooled to −78° C.
  2. temperatureto warm to rt overnight
  3. customthe layers were separated
  4. extractionthe aqueous layer was re-extracted with t-BuOMe
  5. washThe combined organic extracts were washed with brine
  6. dry with materialdried (Na2SO4)
  7. customevaporated to dryness
  8. customPurification by column chromatography (SiO2, EtOAc:cyclohexane 1:1)

Sources & evidence

ORD record
ord-37427ea5e4ef49cc85cd21c1ab7cfa77
Source dataset
uspto-grants-2012_06
Patent number
US08198302B2

Reaction notes

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