m-Chloroperbenzoic acid → Catharanthine N-oxide

HRID 428996

Reaction equation

HRID 428996 reaction equation
[CH3:1][CH2:2][C:3]1[C@H:8]2[N:9]3[CH2:11][CH2:12][C:13]4[C:21]5[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=5)[NH:15][C:14]=4[C@@:7]2([C:22]([O:24][CH3:25])=[O:23])[CH2:6][C@@H:5]([CH2:10]3)[CH:4]=1.ClC1C=CC=C(C(OO)=[O:34])C=1>C(Cl)Cl>[CH3:1][CH2:2][C:3]1[C@H:8]2[N@+:9]3([O-:34])[CH2:11][CH2:12][C:13]4[C:21]5[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=5)[NH:15][C:14]=4[C@@:7]2([C:22]([O:24][CH3:25])=[O:23])[CH2:6][C@@H:5]([CH2:10]3)[CH:4]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 5458190(+)-Catharanthine2×

Product 1

HCID 101458260Catharanthine N-oxide

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of catharanthine (Formula III, 200 mg, 0.6 mmol) in dry methylene chloride (2 ml) at −20° C. under a positive atmosphere of argon was added m-chloroperbenzoic acid (132 mg, 0.8 mmol), and the mixture was stirred for 5 minutes. To the catharanthine N-oxide (IIIa; R═COOCH3; R1, R2, R3, and R4=H), thus formed was added a solution of vindoline (IV, 270 mg, 0.6 mmol) in methylene chloride (1 ml) and the mixture was cooled to −60° C. Trifluoroacetic anhydride (0.2 ml, 1.5 mmol) was added to the stirred reaction mixture maintained at −60° C. for 2 hours. After this time, the solvent and excess reagents were removed in vacuo at −20° C. to leave a reddish-brown residue containing the iminium intermediate. The intermediate was characterized by reverse phase high performance liquid chromatography (HPLC) (Waters Radial-Pak C18 or CN cartridge, methanol-H2O-Et3N as solvent system). It was shown that the yield of the iminium intermediate of Formula VI in this reaction exceeded 80%.

Sources & evidence

ORD record
ord-42d7c0a126df4261b7e95628824cc7d4
Source dataset
uspto-grants-2001_11
Patent number
USRE037449E1

Linked notes

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