2-Butene, 1-bromo-3-methyl- → HCID 71499428, compound

HRID 633668Notes

Reaction equation

HRID 633668 reaction equation
[CH3:1][O:2][C:3]1[C@:10]2([CH2:13][CH:14]=[C:15]([CH3:17])[CH3:16])[C:11](=[O:12])[C@@H:6]([C@:7]([CH3:28])([CH2:22][CH2:23][CH:24]=[C:25]([CH3:27])[CH3:26])[C@@H:8]([O:18][CH2:19][O:20][CH3:21])[CH2:9]2)[C:5](=[O:29])[CH:4]=1.[Li+].CC([N-]C(C)C)C.[CH2:38](Br)[CH:39]=[C:40]([CH3:42])[CH3:41]>C1COCC1>[CH3:1][O:2][C:3]1[C@:10]2([CH2:13][CH:14]=[C:15]([CH3:16])[CH3:17])[C:11](=[O:12])[C@@H:6]([C@:7]([CH3:28])([CH2:22][CH2:23][CH:24]=[C:25]([CH3:27])[CH3:26])[C@@H:8]([O:18][CH2:19][O:20][CH3:21])[CH2:9]2)[C:5](=[O:29])[C:4]=1[CH2:38][CH:39]=[C:40]([CH3:42])[CH3:41]

Participants

5

Reactant 3

HCID 700922-Butene, 1-bromo-3-methyl-HCID 2724682Lithium diisopropylamideHCID 71499446HCID 71499446, compound

Product 1

HCID 71499428HCID 71499428, compoundYield 51.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A 1 dram vial equipped with a stir bar is charged with 12.6 mg (0.031 mmol, 1 equiv.) of starting material 50 followed by 660 μL of THF. The solution is cooled to −78° C. prior to the addition of 124 μL of LDA (0.50 M, 0.062 mmol, 2 equiv.). The mixture was then stirred for 20 minutes followed by the addition of 18 μL (0.155 mmol, 5 equiv.) of prenyl bromide. Stirring was continued for an additional 20 minutes at which time the reaction was quenched by the addition of 500 μL of saturated aqueous ammonium chloride. The reaction was transferred to a separatory funnel in diethyl ether, and the organic layer was washed twice with water, dried with MgSO4, and concentrated in vacuo. The crude product was purified by silica gel chromatography (Rf=0.25 in 9:1 hexane:ethyl acetate), affording 7.5 mg (51% yield) of 54 as a clear oil. 1H NMR (500 MHz, CDCl3) δ ppm 5.07 (t, J=7.0 Hz, 1H), 5.04-4.94 (m, 2H), 4.58 (dd, J=7.0, 47.1 Hz, 2H), 3.95 (s, 3H), 3.60 (dd, J=5.3, 11.4 Hz, 1H), 3.33 (s, 3H), 3.25 (s, 1H), 3.13 (d, J=6.4 Hz, 2H), 2.50 (dd, J=6.2, 14.7 Hz, 1H), 2.42-2.28 (m, 2H), 2.25 (dd, J=5.2, 13.4 Hz, 1H), 1.96-1.84 (m, 1H), 1.77 (dd, J=11.5, 13.3 Hz, 1H), 1.71-1.61 (m, 18H), 1.58-1.51 (m, 2H), 1.30-1.23 (m, 2H), 1.18 (dt, J=4.3, 12.8 Hz, 2H), 0.91 (s, 3H). HRMS-ESI (m/z): [M+H]+ calculated for C29H44O5, 473.3262. found 473.3250.

Workup

  1. customA 1 dram vial equipped with a stir bar
  2. stirringStirring
  3. waitwas continued for an additional 20 minutes at which time
  4. customthe reaction was quenched by the addition of 500 μL of saturated aqueous ammonium chloride
  5. customThe reaction was transferred to a separatory funnel in diethyl ether
  6. washthe organic layer was washed twice with water
  7. dry with materialdried with MgSO4
  8. concentrationconcentrated in vacuo
  9. customThe crude product was purified by silica gel chromatography (Rf=0.25 in 9:1 hexane:ethyl acetate)

Sources & evidence

ORD record
ord-3eba19654b1f4e26bae25a75dfb34e20
Source dataset
uspto-grants-2016_04
Patent number
US09321713B2

Reaction notes

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