Lithium Chloride → 1-(t-Butyloxycarbonyl)-4-(4-methylbenzothiazol-2-yl)-2-methyl-1,2,5,6-tetrahydropyridine

HRID 1760628Notes

Reaction equation

HRID 1760628 reaction equation
Cl[C:2]1[S:3][C:4]2[CH:10]=[CH:9][CH:8]=[C:7]([CH3:11])[C:5]=2[N:6]=1.[C:12]([O:16][C:17]([N:19]1[CH2:24][CH2:23][C:22](S(C(F)(F)F)(=O)=O)=[CH:21][CH:20]1[CH3:32])=[O:18])([CH3:15])([CH3:14])[CH3:13].C[Sn](C)C.C[Sn](C)C.[Cl-].[Li+]>O1CCOCC1.[F-].[K+].C(OCC)(=O)C.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>[C:12]([O:16][C:17]([N:19]1[CH2:24][CH2:23][C:22]([C:2]2[S:3][C:4]3[CH:10]=[CH:9][CH:8]=[C:7]([CH3:11])[C:5]=3[N:6]=2)=[CH:21][CH:20]1[CH3:32])=[O:18])([CH3:15])([CH3:13])[CH3:14]

Participants

9

Reactant 4

HCID 433294Lithium ChlorideHCID 20498602-Chloro-4-methylbenzothiazoleHCID 6327618HexamethylditinHCID 225958741-(t-Butyloxycarbonyl)-2-methyl-4-trifluoromethanesulfonyl-1,2,5,6-tetrahydropyridine

Product 1

HCID 225958521-(t-Butyloxycarbonyl)-4-(4-methylbenzothiazol-2-yl)-2-methyl-1,2,5,6-tetrahydropyridineYield 66%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolventHCID 522689Potassium FluorideSolvent

Conditions

Temperature
20 °C

Procedure

Scheme IIA, Step A: To a mixture of 2-chloro-4-methylbenzothiazole (1.052 g, 5.73 mmol) in 1,4-dioxane (60 mL) was added 1-(t-butyloxycarbonyl)-2-methyl-4-trifluoromethanesulfonyl-1,2,5,6-tetrahydropyridine (2.077 g, 6.01 mmol), hexamethylditin (1.876 g, 5.73 mmol), tetrakis(triphenylphosphine)palladium (0.331 g, 0.286 mmol) and lithium chloride (0.729 g, 17.2 mmol). The mixture was heated at reflux for 20 hours, then cooled to 20° C. and diluted with saturated potassium fluoride and ethyl acetate. The mixture was stirred for 2 hours, then partitioned, and the organics were washed with brine dried over sodium sulfate and evaporated. The residue was chromatographed over silica gel (hexanes/50% ethyl acetate in hexanes gradient elution) to give the intermediate title compound as a yellow amorphous solid (1.3 g, 66%). FDMS m/e=345 (M++1).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 20 hours
  3. custompartitioned
  4. washthe organics were washed with brine
  5. dry with materialdried over sodium sulfate
  6. customevaporated
  7. customThe residue was chromatographed over silica gel (hexanes/50% ethyl acetate in hexanes gradient elution)

Sources & evidence

ORD record
ord-714d91caefa74a9693333b023496e00a
Source dataset
uspto-grants-2005_01
Patent number
US06844344B2

Reaction notes

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