N-Methylaniline → HCID 69929501, compound

HRID 2120980Notes

Reaction equation

HRID 2120980 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]CC2C=CC(Cl)=CC=2)[O:14][C@@H:11]([O:12][CH3:13])[C@@H:10]1[O:35][Si:36]([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:38])[CH3:37])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CNC1C=CC=CC=1.CC([O-])(C)C.[Na+]>CC([O-])=O.CC([O-])=O.[Pd+2].[Cl-].[Cl-].[Zn+2]>[CH2:1]([O:8][C@H:9]1[C@H:16]([O:17][CH2:18][C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[C@@H:15]([CH2:25][OH:26])[O:14][C@@H:11]([O:12][CH3:13])[C@@H:10]1[O:35][Si:36]([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:38])[CH3:37])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 7515N-MethylanilineHCID 23676156Sodium t-butoxideHCID 69929968HCID 69929968, compound

Product 1

HCID 69929501HCID 69929501, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 3007855ZincchlorideCatalyst

Procedure

The general procedure C using 22 (0.123 g, 0.20 mmol), N-methylaniline (26 μL, 0.24 mmol), Pd(OAc)2 (0.9 mg, 0.004 mmol), (o-biphenyl)P(t-Bu)2 (2.4 mg, 0.008 mmol) and NaOtBu (26.9 mg, 0.28 mmol) for 12 h at room temperature afforded a yellow oil. Cleavage of the aminated intermediate with ZnCl2 (240 1L 1.0 M in Et2O, 0.240 mmol) using general procedure D gave 78.2 mg (80%) of 28 as a colorless oil after purification by flash column chromatography on silica gel (25% EtOAc/Hexanes). [α]24D: −28.8° (c 1.32, CH2Cl2); IR (thin film) 3475, 2954, 2855, 1071 cm−1; 1H-NMR (CDCl3) δ 7.38-7.24 (m, 10H), 4.94 (d, J=11.3 Hz, 1H), 4.89 (d, J=11.3 Hz, 1H), 4.82 (d, J=11.0 Hz, 1H), 4.64 (d, J=10.7 Hz, 1H), 4.18 (d, J=7.3 Hz, 1H), 3.91-3.88 (m, 1H), 3.76-3.72 (m, 1H), 3.61-3.49 (m, 6H), 3.42-3.38 (m, 1H), 2.04-2.02 (m, 1H), 0.92 (s, 9H), 0.13 (s, 3H), 0.09 (s, 3H); 13C-NMR (CDCl3) δ 138.7, 138.1, 128.6, 128.4, 128.2, 128.1, 127.6, 127.5, 105.0, 85.7, 78.0, 75.7, 75.4, 75.2, 62.1, 57.4, 26.1, 18.4, −4.1, −4.2; FAB MS m/z (M+Na)+: calcd 511.2492, obsd 511.2492.

Workup

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

Sources & evidence

ORD record
ord-df9bccf4082649b5b6ba5251082cdbc8
Source dataset
uspto-grants-2004_02
Patent number
US06693178B2

Reaction notes

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