Morpholine → HCID 11373402, compound

HRID 2120978Notes

Reaction equation

HRID 2120978 reaction equation
[C:1]([O:4][C@@H:5]1[C@@H:12]([O:13][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C@H:11]([O:21][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[C@@H:10]([CH2:29][O:30]CC2C=CC(Cl)=CC=2)[O:9][C@H:6]1[O:7][CH3:8])(=[O:3])[CH3:2].N1CCOCC1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].Cl[Sn](Cl)(Cl)Cl>CC([O-])=O.CC([O-])=O.[Pd+2]>[C:1]([O:4][C@@H:5]1[C@@H:12]([O:13][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C@H:11]([O:21][CH2:22][C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)[C@@H:10]([CH2:29][OH:30])[O:9][C@H:6]1[O:7][CH3:8])(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 8083MorpholineHCID 24287Tin tetrachlorideHCID 62657Potassium Phosphate, TribasicHCID 11341697HCID 11341697, compound

Product 1

HCID 11373402HCID 11373402, compoundYield 87.2%

Reagents, catalysts & solvents 1

HCID 167845palladium(II) acetateCatalyst

Procedure

The general procedure C using 20 (73.1 mg, 0.135 mmol), morpholine (14.1 μL, 0.162 mmol), Pd(OAc)2 (1.2 mg, 0.0054 mmol), 1-(N,N-dimethylamino)-1′-(dicyclohexylphosphino) biphenyl (5.4 mg, 0.0054 mmol) and K3PO4 (40.0 mg, 0.189 mmol) for 12 h at 100° C. afforded a yellow oil. Cleavage of the aminated intermediate with SnCl4 (162 μL 1.0 M in CH2Cl2, 0.162 mmol) using general procedure D gave 49.0 mg (87%) of 26 as a white solid after purification by flash column chromatography on silica gel (50% EtOAc/Hexanes). [α]24D: −23.5° (c 3.24, CH2Cl2); IR (thin film) 3474, 2879, 1747, 1234, 1082 cm−1; 1H-NMR (CDCl3) δ 7.37-7.26 (m, 10H), 5.00-4.92 (m, 1H), 4.85 (d, J=11.0 Hz, 1H), 4.83 (d, J=11.9 Hz, 1H), 4.69 (d, J=11.0 Hz, 1H), 4.67 (d, J=11.0 Hz, 1H), 4.34 (d, J=7.9 Hz, 1H), 3.92-3.88 (m, 1H), 3.77-3.69 (m, 3H), 3.49 (s, 3H), 3.42-3.40 (m, 1H), 1.98 (s, 3H); 13C-NMR (CDCl3) δ 169.8, 138.2, 137.9, 128.7, 128.6, 128.2, 128.1, 128.0, 127.9, 102.1, 82.7, 77.7, 75.4, 75.3, 75.2, 73.2, 61.9, 57.1, 21.1; FAB MS m/z (M+Na)+: calcd 439.1733, obsd 439.1730.

Workup

  1. customfor 12 h
  2. customat 100° C.
  3. customafforded a yellow oil

Sources & evidence

ORD record
ord-c59ba3b8faeb4ea59e28d98bc46cea48
Source dataset
uspto-grants-2004_02
Patent number
US06693178B2

Reaction notes

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