Palladium-Catalyzed Allylic Substitution Using in Situ Generated Allylindium Reagents

Abstract

It was found that in situ generated allylindium reagent from the reaction of allyl halides with indium is the efficient nucleophile for Pd-catalyzed allylic substitution to produce 1,5-dienes in good yield.

Key words

allylations - catalysis - indium - palladium - substitutions

References

• 1a Tsuji J. Palladium Reagents and Catalysts   John Wiley & Sons; Chichester: 1995.  p.290-422  
• 1b Godleski SA. In Comprehensive Organic Synthesis   Vol. 4:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  p.585 
• 1c Tsuji J. Tetrahedron  1986,  42:  4361 
• 1d Trost BM. Tetrahedron  1977,  33:  2615 
• 1e Heumann A. In Transition Metals for Organic Synthesis   Vol 1:  Beller M. Bolm C. Wiley-VHC; Weinheim: 1998.  p.251 
• 2a Trost BM. Acc. Chem. Res.  1980,  13:  385 
• 2b Wade PA. Morrow SD. Hardinger SA. J. Org. Chem.  1982,  47:  365 
• 2c Tsuji J. Pure Appl. Chem.  1986,  58:  869 
• 2d Tsuji J. Minami L. Acc. Chem. Res.  1987,  20:  140 
• 3a Castanet Y. Petit T. Tetrahedron Lett.  1979,  20:  3221 
• 3b Temple JS. Schwartz J. J. Am. Chem. Soc.  1980,  102:  7381 
• 3c Hayashi T. Konishi M. Yokota K. Kumada M. J. Chem. Soc., Chem. Commun.  1981,  313 
• 3d Matsushita H. Negishi E. J. Am. Chem. Soc.  1981,  103:  2882 
• 3e Godleski SA. Gundlach KB. Ho HY. Keinan E. Frolow F. Organometallics  1984,  3:  21 
• 3f Hayashi T. Konishi M. Kumada M. J. Chem. Soc., Chem. Commun.  1984,  107 
• 4a Trost BM. Keinan E. Tetrahedron Lett.  1980,  21:  2595 
• 4b Godschalx J. Stille JK. Tetrahedron Lett.  1980,  21:  2599 
• 4c Goliaszewski A. Schwartz J. J. Am. Chem. Soc.  1984,  106:  5028 
• 4d Goliaszewski A. Schwartz J. Tetrahedron  1985,  41:  5779 
• 5a Lee PH. Bang K. Lee K. Lee C.-H. Chang S. Tetrahedron Lett.  2000,  41:  7521 
• 5b Lee PH. Ahn H. Lee K. Sung S.-Y. Kim S. Tetrahedron Lett.  2001,  42:  37 
• 5c Lee PH. Sung S.-Y. Lee K. Org. Lett.  2001,  3:  3201 
• 5d Lee PH. Lee K. Kim S. Org. Lett.  2001,  3:  3205 
• 5e Lee PH. Lee K. Chang S. Synth. Commun.  2001,  31:  3189 
• 5f

  Lee, P. H.; Lee, K.; Sung, S.-Y.; Chang, S. J. Org. Chem. 2001, 66, in press

• 6 Chan TH. Yang Y. J. Am. Chem. Soc.  1999,  121:  3228 ; and references therein

7

Representative experimental procedure: To a solution of Pd₂(dba)₃CHCl₃ (5.2 mg, 1 mol%) and tri-o-tolylphosphine (12.2 mg, 8 mol%) in THF (1 mL) was added trans-cinnamyl methyl carbonate (96 mg, 0.5 mmol) at r.t. under a nitrogen atmosphere. After 15 min, allylindium reagent [in situ generated from allyl bromide (91 mg, 0.75 mmol) and indium (57 mg, 0.5 mmol) in THF (1 mL)] was added and the mixture was stirred at 65 °C for 24 h. The reaction mixture was quenched with saturated aqueous NaHCO₃. The aqueous layer was extracted with ether (3 × 15 mL), and the combined organic layers were washed with water and brine, dried with MgSO₄, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography using n-hexane to give trans-1-phenyl-1,5-hexadiene (71 mg, 90%): ¹H NMR (CDCl₃, 400 MHz) δ 7.34 (2 H, d, J = 7.4 Hz), 7.29 (2 H, t, J = 7.9 Hz), 7.19 (1 H, t, J = 7.1 Hz), 6.41 (1 H, d, J = 15.9 Hz), 6.23 (1 H, dt, J = 15.7, 6.6 Hz), 5.88 (1 H, tt, J = 10.4, 6.6 Hz), 5.06 (1 H, d, J = 17.2 Hz), 4.99(1 H, d, J = 9.7 Hz), 2.33-2.23 (4 H, m); ¹³C NMR (CDCl₃, 100 MHz) δ 138.1, 137.8, 130.2, 130.1, 128.5, 126.9, 125.9, 114.9, 33.6, 32.4; HRMS (EI) calcd for C₁₂H₁₄ 158.1096, found 158.1095.