Tri-o-tolylphosphine → HCID 70193441, compound

HRID 1815993Notes

Reaction equation

HRID 1815993 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][Si:9]([CH:16]([CH3:18])[CH3:17])([CH:13]([CH3:15])[CH3:14])[CH:10]([CH3:12])[CH3:11])=[CH:4][CH:3]=1.[CH2:19]([O:26][C:27]([C:29](=[CH2:35])[CH2:30][C:31]([O:33][CH3:34])=[O:32])=[O:28])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.CCN(C(C)C)C(C)C>C(#N)CC.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH:10]([Si:9]([CH:16]([CH3:18])[CH3:17])([CH:13]([CH3:15])[CH3:14])[O:8][C:5]1[CH:6]=[CH:7][C:2]([CH:35]=[C:29]([C:27]([O:26][CH2:19][C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)=[O:28])[CH2:30][C:31]([O:33][CH3:34])=[O:32])=[CH:3][CH:4]=1)([CH3:12])[CH3:11]

Participants

7

Reactant 4

HCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 536194(4-Bromo-phenoxy)-triisopropylsilaneHCID 53688615HCID 53688615, compound

Product 1

HCID 70193441HCID 70193441, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 7854PropionitrileSolvent

Procedure

A solution of 4-bromo-1-(triisopropylsilyloxy)benzene (33.23 g, 100 mmole), methyl 3-(benzyloxycarbonyl)-3-butenoate (28.11 g, 120 mmole), Pd(OAc)2 (2.24 g, 10 mmole), P(o-tolyl)3 (6.09 g, 20 mmole), and (i-Pr)2NEt (34.8 mL, 200 mmole) in propionitrile (350 mL) was deoxygenated (3×evacuation/N2 purge cycles) then was heated to reflux. After 18 hr the mixture was concentrated, and the residue was chromatographed on silica gel (10% EtOAc/hexanes) to give a yellow oil. The oil was taken up in 5% EtOAc/hexanes (100 mL), and the solution was allowed to stand at RT. After 72 hr the mixture was filtered and the filtrate was concentrated to give crude methyl (±)-4-(4-triisopropylsilyloxyphenyl)-3-(benzyloxycarbonyl)-3-butenoate as a mixture of olefin isomers. This was used immediately in the next step.

Workup

  1. custom(3×evacuation/N2 purge cycles)
  2. temperaturethen was heated to reflux
  3. concentrationAfter 18 hr the mixture was concentrated
  4. customthe residue was chromatographed on silica gel (10% EtOAc/hexanes)
  5. customto give a yellow oil
  6. customto stand at RT
  7. filtrationAfter 72 hr the mixture was filtered
  8. concentrationthe filtrate was concentrated

Sources & evidence

ORD record
ord-7f2af385076a4bd89d3bf0ce44eeef1b
Source dataset
uspto-grants-2005_04
Patent number
US06881736B1

Reaction notes

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