N-Methylaniline → HCID 69928110, compound

HRID 2120981Notes

Reaction equation

HRID 2120981 reaction equation
[CH2:1]([O:8][C@H:9]1[C@H:16]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@@H:15]([CH2:25][O:26][Si:27]([C:40]([CH3:43])([CH3:42])[CH3:41])([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[O:14][C@@H:11]([O:12][CH3:13])[C@@H:10]1[O:44]CC1C=CC(Cl)=CC=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CNC1C=CC=CC=1.CC([O-])(C)C.[Na+].Cl[Sn](Cl)(Cl)Cl>CC([O-])=O.CC([O-])=O.[Pd+2]>[CH2:1]([O:8][C@H:9]1[C@H:16]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@@H:15]([CH2:25][O:26][Si:27]([C:40]([CH3:42])([CH3:41])[CH3:43])([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C:34]2[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=2)[O:14][C@@H:11]([O:12][CH3:13])[C@@H:10]1[OH:44])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 7515N-MethylanilineHCID 24287Tin tetrachlorideHCID 23676156Sodium t-butoxideHCID 69928452HCID 69928452, compound

Product 1

HCID 69928110HCID 69928110, compoundYield 81%

Reagents, catalysts & solvents 1

HCID 167845palladium(II) acetateCatalyst

Procedure

The general procedure C using 23 (56.8 mg, 0.077 mmol), N-methylaniline (10 μL, 0.092 mmol), Pd(OAc)2 (0.7 mg, 0.003 mmol), (o-biphenyl)P(t-Bu)2 (1.8 mg, 0.006 mmol) and NaOtBu (10.4 mg, 0.11 mmol) for 12 h at room temperature afforded a yellow oil. Cleavage of the aminated intermediate with SnCl4 (92 μL 1.0 M in CH2Cl2, 0.092 mmol) using general procedure D gave 38.0 mg (81%) of 29 as a colorless oil after purification by flash column chromatography on silica gel (25% EtOAc/Hexanes). [α]24D: −13.60 (c 6.02, CH2Cl2); IR (thin film) 3456, 3070, 2930, 1113, 1055 cm−1; 1H-NMR (CDCl3) δ 7.89 (dd, J=0.6, 6.7 Hz, 2H), 7.83 (dd, J=0.9, 6.7 Hz, 2H), 7.54-7.33 (m, 16H), 5.0 (d, J=11.3 Hz, 1H), 5.04 (d, J=11.0 Hz, 1H), 5.01 (d, J=11.0 Hz, 1H), 4.84 (d, J=11.0 Hz, 1H), 4.32 (d, J=7.6 Hz, 1H), 4.10-4.04 (m, 2H), 3.91 (dd, J=9.2, 9.2 Hz, 1H), 3.76-3.67 (m, 5H), 3.51-3.46 (m, 1H), 2.83 (br s, 1H), 1.18 (s, 9H); 13C-NMR (CDCl3) δ 138.9, 138.4, 136.2, 135.8, 133.9, 133.3, 129.9, 128.8, 128.7, 128.3, 128.2, 128.0, 127.8, 103.8, 84.8, 77.7, 76.2, 75.6, 75.4, 75.0, 62.9, 56.9, 27.0, 19.6; FAB MS m/z (M+Na)+: calcd 635.2805, obsd 635.2804.

Workup

  1. customfor 12 h
  2. customat room temperature
  3. customafforded a yellow oil

Sources & evidence

ORD record
ord-f95908f5594e454dab6d8385b0d88202
Source dataset
uspto-grants-2004_02
Patent number
US06693178B2

Reaction notes

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