Triphenylphosphine → tert-butyl(dimethyl)silyl [(2R)-8-methoxy-3,4-dihydro-2H-chromen-2-yl]methyl ether

HRID 47947Notes

Reaction equation

HRID 47947 reaction equation
[Si:1]([O:8][CH2:9][C@@H:10]([OH:22])[CH2:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([O:19][CH3:20])[C:14]=1O)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1(C)C=CC=CC=1>[CH3:20][O:19][C:15]1[CH:16]=[CH:17][CH:18]=[C:13]2[C:14]=1[O:22][C@@H:10]([CH2:9][O:8][Si:1]([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:2])[CH3:3])[CH2:11][CH2:12]2

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 114161542-((3S)-4-{[tert-butyl(dimethyl)silyl]oxy}-3-hydroxybutyl)-6-methoxyphenol

Product 1

HCID 11404073tert-butyl(dimethyl)silyl [(2R)-8-methoxy-3,4-dihydro-2H-chromen-2-yl]methyl etherYield 76%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 2-((3S)-4-{[tert-butyl(dimethyl)silyl]oxy}-3-hydroxybutyl)-6-methoxyphenol (6.90 g, 21.1 mmol) in toluene (250 mL) cooled to 0° C. is added triphenylphosphine (6.10 g, 23.2 mmol) followed by dropwise addition of diethyl azodicarboxylate (4.05 g, 23.2 mmol). The reaction mixture is allowed to stir at room temperature for 15 min. The reaction-mixture is quenched by the addition of water (300 mL). The aqueous layer is separated and extracted with diethyl ether (2×150 mL). The combined organic extracts are washed with water (200 mL), aqueous sodium chloride (300 mL), dried (magnesium sulfate) and the solvent is removed in vacuo to give a crude oil. Purification by flash column chromatography (silica, ethyl acetate:hexanes 1:4) provided 4.94 g (76%, 40% ee) of tert-butyl(dimethyl)silyl [(2R)-8-methoxy-3,4-dihydro-2H-chromen-2-yl]methyl ether as a colorless oil. [α]D25=−25.84 (c 10.82 in chloroform, 40% ee); Rf=0.68 (silica, ethyl acetate:hexanes 1:4); Anal. Calcd. for C17H28O3Si.0.1H2O: C, 65.8; H, 9.16. Found: C, 65.75; H, 8.88.

Workup

  1. customThe reaction-mixture is quenched by the addition of water (300 mL)
  2. customThe aqueous layer is separated
  3. extractionextracted with diethyl ether (2×150 mL)
  4. washThe combined organic extracts are washed with water (200 mL), aqueous sodium chloride (300 mL)
  5. dry with materialdried (magnesium sulfate)
  6. customthe solvent is removed in vacuo
  7. customto give a crude oil
  8. customPurification by flash column chromatography (silica, ethyl acetate:hexanes 1:4)

Sources & evidence

ORD record
ord-01e87531b147495abcf073dd9743ee65
Source dataset
uspto-grants-2004_03
Patent number
US06700001B2

Reaction notes

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