tert-Butyl bromoacetate → HCID 72713821, compound

HRID 571148Notes

Reaction equation

HRID 571148 reaction equation
[CH3:1][C:2]1([CH3:12])[O:7][C@H:6](/[CH:8]=[CH:9]\[CH2:10][OH:11])[CH2:5][CH2:4][O:3]1.[C:13]([O:17][C:18](=[O:21])[CH2:19]Br)([CH3:16])([CH3:15])[CH3:14].O.[OH-].[Cs+]>C(#N)C.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[CH3:1][C:2]1([CH3:12])[O:7][C@H:6](/[CH:8]=[CH:9]\[CH2:10][O:11][CH2:19][C:18]([O:17][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:21])[CH2:5][CH2:4][O:3]1

Participants

6

Reactant 3

HCID 79177tert-Butyl bromoacetateHCID 23679066Caesium hydroxide--water (1/1/1)HCID 89871230HCID 89871230, compound

Product 1

HCID 72713821HCID 72713821, compoundYield 97%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 6342AcetonitrileSolvent

Procedure

To a round bottom flask charged with activated molecular sieves (6.0 g) was added a solution of substrate, (S,Z)-3-(2,2-dimethyl-1,3-dioxan-4-yl)prop-2-en-1-ol (9.0 g, 52.0 mmol) in acetonitrile (150 mL), followed by t-butylbromoacetate (9.90 mL, 67.2 mmol), tetrabutylammonium iodide (2.0 g, 5.2 mmol) and cesium hydroxide monohydrate (13.1 g, 78.0 mmol) at room temperature. The reaction was allowed to stir for 6 h. The solid was filtered out and the solvent was concentrated under vacuum; the residue was purified by flash column chromatography (5% ethyl acetate/hexanes) to afford 3 (14.4 g, 97% yield) as a colorless oil. Rf=0.57 (30% ethyl acetate/hexanes). [α]23D=+ 22.9 (c 1.29, CHCl3) 1H NMR (300 MHz, Chloroform-d) δ 5.72-5.51 (m, 2H), 4.77-4.65 (m, 1H), 4.26-4.09 (m, 2H), 4.01 (dd, J=17.3, 2.6 Hz, 1H), 3.93 (d, J=3.6 Hz, 2H) 3.82 (ddd, J=11.8 Hz, 5.4 Hz, 1.4 Hz, 1H), 1.79-1.65 (m, 1H), 1.48 (s, 3H), 1.46 (s, 10H), 1.37 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 169.5, 134.1, 127.7, 98.3, 81.5, 67.6, 66.8, 65.5, 59.5, 31.1, 29.9, 28.0, 19.1.

Workup

  1. additionTo a round bottom flask charged with activated molecular sieves (6.0 g)
  2. filtrationThe solid was filtered out
  3. concentrationthe solvent was concentrated under vacuum
  4. customthe residue was purified by flash column chromatography (5% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-ace3987cb3fe40119fcce899372cacfa
Source dataset
uspto-grants-2015_05
Patent number
US09024038B2

Reaction notes

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