Morpholine → HCID 69929508, compound

HRID 2120979Notes

Reaction equation

HRID 2120979 reaction equation
[C:1]([O:9][C@@H:10]1[C@@H:17]([O:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C@H:16]([O:26][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C@@H:15]([CH2:34][O:35]CC2C=CC(Cl)=CC=2)[O:14][C@H:11]1[O:12][CH3:13])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.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:9][C@@H:10]1[C@@H:17]([O:18][CH2:19][C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)[C@H:16]([O:26][CH2:27][C:28]2[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=2)[C@@H:15]([CH2:34][OH:35])[O:14][C@H:11]1[O:12][CH3:13])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 8083MorpholineHCID 24287Tin tetrachlorideHCID 62657Potassium Phosphate, TribasicHCID 69929399HCID 69929399, compound

Product 1

HCID 69929508HCID 69929508, compoundYield 79%

Reagents, catalysts & solvents 1

HCID 167845palladium(II) acetateCatalyst

Procedure

The general procedure C using 21 (70.3 mg, 0.117 mmol), morpholine (12.2 μL, 0.140 mmol), Pd(OAc)2 (1.0 mg, 0.0046 mmol), 1-(N,N-dimethylamino)-1′-(dicyclohexylphosphino) biphenyl (1.8 mg, 0.0046 mmol) and K3PO4 (34.8 mg, 0.164 mmol) for 12 h at 100° C. afforded a yellow oil. Cleavage of the aminated intermediate with SnCl4 (140 μL 1.0 M in CH2Cl2, 0.140 mmol) using general procedure D gave 44.0 mg (79%) of 27 as a colorless oil after purification by flash column chromatography on silica gel (50% EtOAc/Hexanes). [α]24D: −28.1° (c 3.24, CH2Cl2); IR (thin film) 3454, 2878, 1726, 1269, 1086 cm−1; 1H-NMR (CDCl3) δ 8.04 (d, J=8.2 Hz, 2H), 7.59 (t, J=8.5 Hz, 1H), 7.38-7.32 (m, 4H), 7.15 (s, 4H), 5.26 (dd, J=8.2, 9.4 Hz, 1H), 4.88 (d, J=11.0 Hz, 1H), 4.78 (d, J=11.0 Hz, 1H), 4.70 (d, J=11.0 Hz, 1H), 4.69 (d, J=11.3 Hz, 1H), 4.51 (d, J=7.9 Hz, 1H), 3.96-3.94 (m, 1H), 3.88 (dd, J=9.2, 9.5 Hz, 1H), 3.80-3.75 (m, 2H), 3.51-3.48 (m, 4H), 2.09-2.07 (m, 1H); 13C-NMR (CDCl3) δ 165.4, 138.0, 137.9, 133.3, 130.0, 128.7, 128.6, 128.5, 128.3, 128.2, 127.9, 102.2, 82.7, 77.8, 75.5, 75.3, 73.9, 62.0, 57.2; FAB MS m/z (M+Na)+: calcd 501.1890, obsd 501.1888.

Workup

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

Sources & evidence

ORD record
ord-5a66472d351d4a20bf39e4f755648040
Source dataset
uspto-grants-2004_02
Patent number
US06693178B2

Reaction notes

Loading…