Ammonium Chloride → HCID 89965892, compound

HRID 1468719Notes

Reaction equation

HRID 1468719 reaction equation
Br[C:2]1[S:3][C:4]2[C:10]([O:11][S:12]([C:15]([F:18])([F:17])[F:16])(=[O:14])=[O:13])=[C:9]([C@H:19]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])[C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:8]([CH3:30])=[CH:7][C:5]=2[N:6]=1.[CH:31]([Sn](CCCC)(CCCC)CCCC)=[CH2:32].[NH4+].[Cl-]>[Cu]I.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.CN(C=O)C>[C:26]([O:25][C@@H:19]([C:9]1[C:8]([CH3:30])=[CH:7][C:5]2[N:6]=[C:2]([CH:31]=[CH2:32])[S:3][C:4]=2[C:10]=1[O:11][S:12]([C:15]([F:18])([F:17])[F:16])(=[O:14])=[O:13])[C:20]([O:22][CH2:23][CH3:24])=[O:21])([CH3:29])([CH3:28])[CH3:27]

Participants

7

Reactant 3

HCID 25517Ammonium ChlorideHCID 81998TributylvinyltinHCID 86699785(S)-ethyl 2-(2-bromo-5-methyl-7-(trifluoromethylsulfonyloxy)benzo[d]thiazol-6-yl)-2-tert-butoxyacetate

Product 1

HCID 89965892HCID 89965892, compoundYield 77%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
65 °C

Procedure

A microwave vial was charged with CuI (9.4 mg, 49 μmol), Pd(PPh3)4 (29 mg, 25 μmol), and 32 (250 mg, 0.494 mmol). The vial was sealed and placed under a vacuum. The vessel was backfilled with argon and charged with DMF (1.0 mL) followed by vinyl-(tri-n-butyl)tin (173 μL, 0593 mmol). Reaction was stirred at 65° C. for 1 h, then cooled to 23° C. Sat. aq. NH4Cl (40 mL) was added and the reaction was extracted with EtOAc (2×20 mL). Combined organic layers were dried (Na2SO4), filtered, and concentrated. Hexane was added, and the slurry was concentrated again. The residue was treated with PhH and purified by silica gel column chromatography (eluent: Hexanes/Ethyl Acetate) giving 91A (173 mg, 77% yield). 1H-NMR: 400 MHz, (CDCl3) δ: 7.80 (s, 1H), 7.00 (dd, J=18.6, 10.9 Hz, 1H), 6.24 (d, J=18.6 Hz, 1H), 5.82 (d, J=10.9 Hz, 1H), 5.60 (s, 1H), 4.24-4.06 (m, 2H), 2.54 (s, 3H), 1.22 (s, 9H), 1.19 (t, J=6.8 Hz, 3H). 19F-NMR: 376 MHz, (CDCl3) δ: 73.8.

Workup

  1. customThe vial was sealed
  2. customReaction
  3. temperaturecooled to 23° C
  4. extractionthe reaction was extracted with EtOAc (2×20 mL)
  5. dry with materialCombined organic layers were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. additionHexane was added
  9. concentrationthe slurry was concentrated again
  10. additionThe residue was treated with PhH
  11. custompurified by silica gel column chromatography (eluent: Hexanes/Ethyl Acetate)

Sources & evidence

ORD record
ord-da144e5245c24630b806c6382427015f
Source dataset
uspto-grants-2015_04
Patent number
US09006229B2

Reaction notes

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