Allyl bromide → HCID 10388413, compound

HRID 2416183Notes

Reaction equation

HRID 2416183 reaction equation
C([Si](C)(C)[O:6][C:7]([C:16]1[CH:21]=[CH:20][C:19]([CH2:22][S:23]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)(=[O:25])=[O:24])=[CH:18][CH:17]=1)([C:12]([F:15])([F:14])[F:13])[C:8]([F:11])([F:10])[F:9])(C)(C)C.[Li][CH2:35][CH2:36][CH2:37]C.CN1C(=O)N(C)CCC1.C(Br)C=C>C1COCC1>[F:15][C:12]([F:14])([F:13])[C:7]([C:16]1[CH:17]=[CH:18][C:19]([CH:22]([S:23]([C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)(=[O:24])=[O:25])[CH2:37][CH:36]=[CH2:35])=[CH:20][CH:21]=1)([OH:6])[C:8]([F:10])([F:11])[F:9]

Participants

6

Reactant 4

HCID 7841Allyl bromideHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-HCID 22639167HCID 22639167, compoundHCID 178418339Butyllithium

Product 1

HCID 10388413HCID 10388413, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

Tert-Butyl(dimethyl)[2,2,2-trifluoro-1-{4-[(phenylsulfonyl)methyl]phenyl}-1-(trifluoromethyl)ethoxy]silane (378 mg, 0.74 mmol) was dissolved in anhydrous THF (10 mL) under argon and cooled to −78° C. 1.6M BuLi solution in hexanes (0.5 mL, 0.85 mmol) was added and the reaction was allowed to warm to 0° C. After 30 min at 0° C., the reaction was cooled to −78° C. and DMPU (0.26 mL, 2.1 mmol) was added, followed by allyl bromide (0.07 mL, 0.81 mmol). The reaction was allowed to warm to 0° C. and monitored by thin layer chromatography. The reaction was quenched with saturated NH4Cl and diluted with ethyl acetate. The layers were separated and the organic phase was washed with brine, dried (MgSO4), and concentrated in vacuo. Purification by flash chromatography (6:1 hexanes/EtOAc) afforded the protected sulfone as a colorless oil. The sulfone was deprotected as described in Example 2 step 3. Purification by flash chromatography (6:1 hexanes/EtOAc) afforded the title compound as a white solid (266 mg, 82%): mp=148° C. 1H NMR (CDCl3) δ 7.55 (m, 3H), 7.45 (d, 2H), 7.33 (t, 2H), 7.17 (d, 2H), 5.55 (m, 1H), 5.04 (m, 2H), 4.14 (dd, 1H), 3.51 (br s, 1H), 3.21 (m, 1H), 2.93 (m, 1H). Anal. Calc. for C19H16O3SF6: C, 52.06; H, 3.68. Found: 52.04; H, 3.45. HRMS (M+NH4+) Calc.: 456.1068. Found: 456.1075.

Workup

  1. temperatureto warm to 0° C
  2. temperaturethe reaction was cooled to −78° C.
  3. temperatureto warm to 0° C.
  4. customThe reaction was quenched with saturated NH4Cl
  5. additiondiluted with ethyl acetate
  6. customThe layers were separated
  7. washthe organic phase was washed with brine
  8. dry with materialdried (MgSO4)
  9. concentrationconcentrated in vacuo
  10. customPurification by flash chromatography (6:1 hexanes/EtOAc)

Sources & evidence

ORD record
ord-36d111dc229549b9bcf10369ff3c9f02
Source dataset
uspto-grants-2004_11
Patent number
US06822120B2

Reaction notes

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