Sodium Carbonate → HCID 86691562, compound

HRID 514115Notes

Reaction equation

HRID 514115 reaction equation
[F: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>[F: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 86691561HCID 86691561, compound

Product 1

HCID 86691562HCID 86691562, compoundYield 94.2%

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-fluoro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-oxoacetate (1.08 g, 2.64 mmol) in PhMe (20 mL) was cooled to −40° C. (dry ice/CH3CN bath). (R) —CBS catalyst (146 mg, 0.528 mmol) was introduced. Distilled catecholborane (423 μL) was added dropwise over a 5 min period. After 30 min, the reaction was warmed to −20° C. and treated with EtOAc (20 mL). Then 15% Na2CO3 (10 mL) was added. The reaction was warmed to 23° C. and stirred vigorously. The organic phase was collected after 30 min. It was washed (vigorous stirring) with 10 mL portions of 15% Na2CO3 for 30 min each until the layer was colorless. (Early washes tended to be dark greenish-brown). After six such washings, the organic phase was treated with saturated NH4Cl (20 mL) for 30 min. The organic phase was dried (MgSO4), filtered, and concentrated. The residue was treated with hexanes and concentrated again. The material was dissolved in benzene. The solution was wet-loaded onto a 40 g “gold” ISCO silica gel column and purified by flash chromatography (hexane→ethyl acetate) giving the desired product (1.02 g, 94% yield). 1H NMR (400 MHz, CDCl3) δ 8.11-8.06 (m, 2H), 7.67-7.64 (m, 2H), 5.79 (s, 1H), 4.33-4.22 (m, 2H), 2.40 (d, JHF=3.2 Hz, 3H), 1.22 (t, J=7.4 Hz, 3H). 19F NMR (377 MHz, CDCl3) δ−122.6 (app. s, 1F), −73.1 (s, 3F).

Workup

  1. temperatureThe reaction was warmed to 23° C.
  2. customThe organic phase was collected after 30 min
  3. washIt was washed
  4. stirring(vigorous stirring) with 10 mL portions of 15% Na2CO3 for 30 min each until the layer
  5. additionAfter six such washings, the organic phase was treated with saturated NH4Cl (20 mL) for 30 min
  6. dry with materialThe organic phase was dried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. additionThe residue was treated with hexanes
  10. concentrationconcentrated again
  11. dissolutionThe material was dissolved in benzene
  12. custompurified by flash chromatography (hexane→ethyl acetate)

Sources & evidence

ORD record
ord-f840cfa0639b4da393d66b43a0f348d6
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

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