Benzaldehyde → Perfluorophenyl 5-(1-benzylpyrrolidin-2-yl)naphthalene-2-sulfonate

HRID 1473351Notes

Reaction equation

HRID 1473351 reaction equation
FC(F)(F)C(O)=O.[NH:8]1[CH2:12][CH2:11][CH2:10][CH:9]1[C:13]1[CH:22]=[CH:21][CH:20]=[C:19]2[C:14]=1[CH:15]=[CH:16][C:17]([S:23]([O:26][C:27]1[C:32]([F:33])=[C:31]([F:34])[C:30]([F:35])=[C:29]([F:36])[C:28]=1[F:37])(=[O:25])=[O:24])=[CH:18]2.[CH:38](=O)[C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].[C@H](O)(C([O-])=O)[C@@H](O)C([O-])=O.[Na+].[K+]>O.C(Cl)Cl.ClCCCl>[CH2:38]([N:8]1[CH2:12][CH2:11][CH2:10][CH:9]1[C:13]1[CH:22]=[CH:21][CH:20]=[C:19]2[C:14]=1[CH:15]=[CH:16][C:17]([S:23]([O:26][C:27]1[C:32]([F:33])=[C:31]([F:34])[C:30]([F:35])=[C:29]([F:36])[C:28]=1[F:37])(=[O:25])=[O:24])=[CH:18]2)[C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1

Participants

8

Reactant 4

HCID 240BenzaldehydeHCID 9357Potassium Sodium TartrateHCID 5049666Sodium triacetoxyborohydrideHCID 86687398Perfluorophenyl 5-(pyrrolidin-2-yl)naphthalene-2-sulfonate 2,2,2-trifluoroacetate

Product 1

HCID 86687401Perfluorophenyl 5-(1-benzylpyrrolidin-2-yl)naphthalene-2-sulfonateYield 97.1%

Reagents, catalysts & solvents 3

HCID 111,2-DichloroethaneSolvent2×HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A 10-mL round-bottom flask was charged with perfluorophenyl 5-(pyrrolidin-2-yl)naphthalene-2-sulfonate 2,2,2-trifluoroacetate (from STEP 2 of INTERMEDIATE KK) (56.79 mg, 0.102 mmol), DCE (509 μl), and benzaldehyde (31.0 μl, 0.306 mmol) to give a suspension. Sodium triacetoxyborohydride (43.2 mg, 0.204 mmol) was added, followed by an additional portion of DCE (509 μl) to thin the mixture. After 1 h, a saturated aq. Rochelle's salt solution (3 mL) and DCM (2 mL) were added, and the resulting mixture was stirred vigorously for 3 h. The mixture was diluted with water and extracted with DCM (3×). The combined organic extracts were dried over sodium sulfate, filtered, and concentrated. The residue was purified by chromatography on a 12-g with 0 to 40% EtOAc/Heptane to give perfluorophenyl 5-(1-benzylpyrrolidin-2-yl)naphthalene-2-sulfonate (52.93 mg, 0.099 mmol, 97% yield) as a clear oil: 1H NMR (400 MHz, DMSO-d6) δ ppm=8.86-8.70 (m, 2H), 8.22-8.10 (m, 2H), 8.00 (dd, J=2.2, 9.1 Hz, 1H), 7.81-7.73 (m, 1H), 7.33-7.26 (m, 4H), 7.25-7.17 (m, 1H), 4.20 (t, J=8.2 Hz, 1H), 3.77 (d, J=13.2 Hz, 1H), 3.20 (d, J=13.2 Hz, 1H), 3.13-3.02 (m, 1H), 2.48-2.40 (m, 1H), 2.33 (q, J=9.2 Hz, 1H), 1.93-1.82 (m, 2H), 1.78-1.60 (m, 1H); m/z (ESI) 534.4 (M+H)+.

Workup

  1. customto give a suspension
  2. extractionextracted with DCM (3×)
  3. dry with materialThe combined organic extracts were dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by chromatography on a 12-g with 0 to 40% EtOAc/Heptane

Sources & evidence

ORD record
ord-81139a062d194bffb7cd68ec0b32d54d
Source dataset
uspto-grants-2015_04
Patent number
US09012443B2

Reaction notes

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