Water → Methyl 4-allyl-3-(4-benzyloxyazepan-1-yl)sulfonyl-benzoate

HRID 1754302Notes

Reaction equation

HRID 1754302 reaction equation
[CH2:1]([O:8][CH:9]1[CH2:15][CH2:14][CH2:13][N:12]([S:16]([C:19]2[CH:20]=[C:21]([CH:26]=[CH:27][C:28]=2Br)[C:22]([O:24][CH3:25])=[O:23])(=[O:18])=[O:17])[CH2:11][CH2:10]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:30]([Sn](CCCC)(CCCC)CCCC)[CH:31]=[CH2:32].CCOC(C)=O.O>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:32]([C:28]1[CH:27]=[CH:26][C:21]([C:22]([O:24][CH3:25])=[O:23])=[CH:20][C:19]=1[S:16]([N:12]1[CH2:13][CH2:14][CH2:15][CH:9]([O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH2:10][CH2:11]1)(=[O:18])=[O:17])[CH:31]=[CH2:30]

Participants

7

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 90628AllyltributylstannaneHCID 118222070methyl 3-(4-benzyloxyazepan-1-yl)Sulfonyl-4-bromo-benzoate

Product 1

HCID 118222059Methyl 4-allyl-3-(4-benzyloxyazepan-1-yl)sulfonyl-benzoateYield 52.8%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

Methyl 3-(4-benzyloxyazepan-1-yl)sulfonyl-4-bromo-benzoate (1.30 g, 2.69 mmol, 1.00 Eq), allyl(tributyl)stannane (1.07 g, 3.23 mmol, 1.20 Eq) LiCl (136.83 mg, 3.23 mmol, 1.20 Eq) and Pd(PPh3)4 (310.85 mg, 269.00 umol, 0.10 Eq) in TOLUENE (20 mL) was de-gassed and then heated to 110° C. for 16 hr under N2. TLC (PE:EtOAc=1:1) showed the starting material and the product was the same spot. The reaction mixture was poured into H2O, extracted with EA. The organic phase was dried over anhydrous Na2SO4, concentrated in vacuum to give a residue, which was purified by column chromatography (silica gel, eluting with PE:EA=1:1) to afford the pure methyl 4-allyl-3-(4-benzyloxyazepan-1-yl)sulfonyl-benzoate (630.00 mg, 1.42 mmol, 52.80% yield) as light yellow solid.

Workup

  1. extractionextracted with EA
  2. dry with materialThe organic phase was dried over anhydrous Na2SO4
  3. concentrationconcentrated in vacuum
  4. customto give a residue, which
  5. customwas purified by column chromatography (silica gel, eluting with PE:EA=1:1)

Sources & evidence

ORD record
ord-f54c1e5123de49fb95c43ec0f3999582
Source dataset
uspto-grants-2015_10
Patent number
US09169212B2

Reaction notes

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