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TCI Practical Example: Intermolecular Allylic C-H Amination Using White Catalyst

We are proud to present the intermolecular allylic C-H Amination of 1-decene and methyl N-(p-toluenesulfonyl)carbamate using White catalyst.

Used Chemicals

• 1,2-Bis(phenylsulfinyl)ethane Palladium(II) Diacetate (= White Catalyst) [B3292]
• 1-Decene [D0028]
• Methyl N-(p-Toluenesulfonyl)carbamate [M2988]
• N,N-Diisopropylethylamine (= DIPEA) [D1599]
• 1,4-Benzoquinone (= BQ) [B0089]
• tert-Butyl Methyl Ether (= MTBE)

Procedure

A stoppered test tube was charged with 1-decene (0.5 g, 3.56 mmol), MTBE (5.4 mL), White catalyst (181 mg, 0.36 mmol), 1,4-benzoquinone (770 mg, 7.12 mmol), methyl N-(p-toluenesulfonyl)carbamate (1.63 g, 7.12 mmol), N,N-diisopropylethylamine (40 μL, 0.21 mmol) were then sequentially added under air. The test tube was capped with a glass stopper and stirred at 40 °C. After 72 h, the reaction mixture was allowed to cool to room temperature. The suspension was filtrated and the insoluble was washed with diethyl ether (30 mL). The filtrate was washed with 5% sodium carbonate aqueous solution (50 mL), and the aqueous layer was extracted with diethyl ether (30 mL). The combined organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by medium pressure preparative chromatography (silica gel, ethyl acetate:hexane = 5:95 – 20:80) to give 1 as a yellow oil (0.73 g, 56%).

Experimenter’s Comments

The reaction mixture was monitored by TLC (ethyl acetate:hexane = 1:3, Rf = 0.58).

Analytical Data

Compound 1

¹H NMR (400 MHz, CDCl₃); δ 7.81 (d, J = 9.2 Hz, 2H), 7.29 (d, J = 7.8 Hz, 2H), 5.78 (m,1H), 5.51 (m, 1H), 4.40 (d, J = 6.4 Hz, 2H), 3.68 (s, 3H), 2.43 (s, 3H), 2.04 (m, 2H), 1.37 (m, 10H), 0.88 (t, J = 6.7 Hz, 3H).

Lead References

• Catalytic Intermolecular Linear Allylic C−H Amination via Heterobimetallic Catalysis
• • S. A. Reed, A. R. Mazzotti, M. C. White, J. Am. Chem. Soc. 2008, 130, 3316.

• A Catalytic, Brønsted Base Strategy for Intermolecular Allylic C−H Amination
• • S. A. Reed, A. R. Mazzotti, M. C. White, J. Am. Chem. Soc. 2009, 131, 11701.

Other References

• syn-1,2-Amino Alcohols via Diastereoselective Allylic C−H Amination
• • K. J. Fraunhoffer, M. C. White, J. Am. Chem. Soc. 2007, 129, 7274.

• Serial Ligand Catalysis:  A Highly Selective Allylic C−H Oxidation
• • M. S. Chen, N. Prabagaran, N. A. Labenz, M. C. White, J. Am. Chem. Soc. 2005, 127, 6970.