1,2-Bis(phenylsulfinyl)ethane Palladium(II) Diacetate

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) [B0991]

Procedure

A test tube with thread　under air 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) and a magnetic stir bar were then sequentially added. The test tube was fitted with a glass stopper, stirred at 45 °C. After 72 h, the reaction mixture was allowed to cool to room temperature. The suspension was filtrated and washed with diethyl ether (30 mL). The filtrate was washed with 5% sodium carbonate aqueous solution (50 mL), and the aqueous phase was extracted with diethyl ether (30 mL). The combined organic phase was dried over sodium sulfate and filtered. The solvent was removed under reduced pressure and the residue was purified by medium pressure preparative chromatography (silica gel, hexane : ethyl acetate = 5 : 95 - 20 : 80), giving 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.

References

• 1) M. S. Chen, N. Prabagaran, N. A. Labenz, M. C. White, J. Am. Chem. Soc. 2005, 127, 6970.
• 2) K. J. Fraunhoffer, N. Prabagaran, L. E. Sirois, M. C. White, J. Am. Chem. Soc. 2006, 128, 9032.
• 3) K. J. Fraunhoffer, M. C. White, J. Am. Chem. Soc. 2007, 129, 7274.