Sodium Carbonate → HCID 86691573, compound

HRID 514161Notes

Reaction equation

HRID 514161 reaction equation
[Br:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([O:12][S:13]([C:16]([F:19])([F:18])[F:17])(=[O:15])=[O:14])=[C:4]([C:20](=[O:26])[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:3]=1[CH3:27].C(=O)=O.CC#N.[B]1OC2C(=CC=CC=2)O1.C([O-])([O-])=O.[Na+].[Na+]>C1(C)C=CC=CC=1.B1(C)OC(C2C=CC=CC=2)(C2C=CC=CC=2)[C@@H]2N1CCC2.CCOC(C)=O>[Br:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([O:12][S:13]([C:16]([F:18])([F:17])[F:19])(=[O:14])=[O:15])=[C:4]([C@H:20]([OH:26])[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:3]=1[CH3:27]

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 6327445BenzcatechinboraneHCID 86587134Acetonitrile dry iceHCID 86691571HCID 86691571, compound

Product 1

HCID 86691573HCID 86691573, compoundYield 75%

Reagents, catalysts & solvents 3

HCID 9838490(R)-2-Methyl-CBS-oxazaborolidineCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-20 °C

Procedure

A solution of ethyl 2-(4-bromo-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-oxoacetate (1.18 g, 2.52 mmol) in PhMe (20 mL) was cooled to −40° C. (dry ice/CH3CN). (R) —CBS catalyst (140 mg, 0.504 mmol) was introduced, followed by distilled catecholborane (neat, 402 μL, 3.77 mmol) over a 5 min period. After 30 min, the reaction was warmed to ˜−20° C. EtOAc (20 mL) was added. Then 15% Na2CO3 (10 mL) was added. The reaction was stirred vigorously as it was warmed to 23° C. overnight. The next day, the organic phase was washed (with vigorous stirring) with more 15% Na2CO3 (10 mL portions for 30 min each) until the washes were colorless. After the fifth wash, the organic phase was washed once with saturated NH4Cl (10 mL) for 10 min, then dried (MgSO4), filtered, and concentrated. The residue was dissolved in hexane and re-concentrated. The residue was treated with benzene, filtered, and wet-loaded onto a silica gel column and purified by flash chromatography (ethyl acetate/hexanes) giving the desired product (886 mg, 75% yield). 1H NMR (400 MHz, CDCl3) δ 8.41 (d, J=8.2 Hz, 1H), 8.09 (d, J=8.6 Hz, 1H), 7.71 (dd, J=8.6, 8.2 Hz, 1H), 7.66 (dd, J=8.6, 8.6 Hz, 1H), 5.84 (d, J=2.4 Hz, 1H), 4.34-4.20 (m, 2H), 3.41 (d, J=2.4 Hz, 1H), 2.63 (s, 3H), 1.22 (t, J=7.0 Hz, 3H). 19F NMR (377 MHz, CDCl3) δ−73.0 (s).

Workup

  1. temperaturewas warmed to 23° C. overnight
  2. washThe next day, the organic phase was washed
  3. stirring(with vigorous stirring) with more 15% Na2CO3 (10 mL portions for 30 min each) until the washes
  4. washAfter the fifth wash
  5. washthe organic phase was washed once with saturated NH4Cl (10 mL) for 10 min
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. dissolutionThe residue was dissolved in hexane
  10. concentrationre-concentrated
  11. additionThe residue was treated with benzene
  12. filtrationfiltered
  13. customwet-loaded onto a silica gel column and purified by flash chromatography (ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-bc2a6d8c8ac447a3843b8e5e46087ecb
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

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