Bis-Functionalization of 1,3-Dienes through 1,4-Conjugate Addition of Amphiphilic Bis-π-Allyl and Related Palladium Intermediates

Abstract

Palladium-catalyzed three-component coupling of allylstannane, allyl chloride and a functionalized diene is described. Regioselective 1,4-functionalization of the Michael acceptor 1,3-diene is accomplished by the amphiphilic bis-π-allylpalladium complex. To the best of our knowledge, this is the first time a functionalized 1,3-butadiene has been used as a Michael acceptor. The scope of the present strategy is further extended to 1,4-allylation–oxyallylation of functionalized dienes.

Key words

palladium - allylation - allyl complexes - coupling - ­Michael addition

• References and Notes

• 1a Balci M. Chem. Rev. 1981; 81: 91
• 1b Davis KM, Carpenter BK. J. Org. Chem. 1996; 61: 4617
• 1c Gollnick K, Griesbeck A. Tetrahedron Lett. 1983; 24: 3303
• 1d Aubry J.-M, Mandard-Cazin B, Rougee M, Bensasson RV. J. Am. Chem. Soc. 1995; 117: 9159
• 1e Mehta G, Uma R. J. Org. Chem. 2000; 65: 1685
• 2a Belleau B, Au-Young Y.-K. J. Am. Chem. Soc. 1963; 85: 64
• 2b Streith J, Augelmann G, Fritz H, Strub H. Tetrahedron Lett. 1982; 23: 1909
• 2c Keck GE, Fleming SA. Tetrahedron Lett. 1978; 4763
• 3a Diels O, Blom JH, Knoll W. Justus Liebigs Ann. Chem. 1925; 443: 242
• 3b Cookson RC, Gilani SS. H, Stevens ID. R. Tetrahedron Lett. 1962; 615
• 3c Giuliano RM, Jordan AD, Gauthier AD, Hoogsteen K. J. Org. Chem. 1993; 58: 4979
• 4a Verboom RC, Perssonand BA, Bäckvall JE. J. Org. Chem. 2009; 69: 3102
• 4b Aranyos A, Szabo KJ, Bäckvall JE. J. Org. Chem. 1998; 63: 2523
• 4c Bäckvall JE. Pure Appl. Chem. 1996; 68: 535
• 4d Bäckvall JE, Nyström JE, Nordberg RE. J. Am. Chem. Soc. 1985; 107: 3676
• 4e Bäckvall JE, Byström SE, Nordberg RE. J. Org. Chem. 1984; 49: 4619
• 4f Bäckvall JE. Pure Appl. Chem. 1983; 55: 1669
• 5a He Z, Yi CS, Donaldson WA. Org. Lett. 2003; 5: 1567
• 5b Gerdin M, Moberg C. Adv. Synth. Catal. 2005; 347: 749
• 5c Kliman LT, Mlynarski SN, Ferris GE, Morken JP. Angew. Chem. Int. Ed. 2012; 51: 521
• 5d Mizutani K, Shinokubo H, Oshima K. Org. Lett. 2003; 5: 3959
• 5e Sasaki Y, Zhong C, Sawamura M, Ito H. J. Am. Chem. Soc. 2010; 132: 1226
• 6a Ely RJ, Morken JP. J. Am. Chem. Soc. 2010; 132: 2534
• 6b Shirakura M, Suginome M. J. Am. Chem. Soc. 2008; 130: 5410
• 6c Gerdin M, Moberg C. Org. Lett. 2006; 14: 2929
• 6d Saha B, RajanBabu TV. Org. Lett. 2006; 8: 4657
• 6e Takimoto M, Mori M. J. Am. Chem. Soc. 2001; 123: 2895
• 6f Kimura M, Ezoe A, Shibata K, Tamaru Y. J. Am. Chem. Soc. 1998; 120: 4033
• 6g Buono G, Siv C, Peiffer G, Triantaphylides C, Denis P, Mortreux A, Petit F. J. Org. Chem. 1985; 50: 1781
• 7a Takaya J, Sasano K, Iwasawa N. Org. Lett. 2011; 13: 1698
• 7b Rozhkov RV, Larock RC. J. Org. Chem. 2010; 75: 4131
• 7c Liao L, Sigman MS. J. Am. Chem. Soc. 2010; 132: 10209
• 8a Wu JY, Stanzl BN, Ritter T. J. Am. Chem. Soc. 2010; 132: 13214
• 8b Wu JY, Moreau B, Ritter T. J. Am. Chem. Soc. 2009; 131: 12915
• 9 Watkins AL, Landis CR. Org. Lett. 2011; 13: 164
• 10a Arndt M, Dindaroglu M, Schmalz HG, Hilt G. Org. Lett. 2011; 13: 6236
• 10b Arndt M, Reinhold A, Hilt G. J. Org. Chem. 2010; 75: 5203
• 10c Hilt G, du Mesnil FX, Luers S. Angew. Chem. Int. Ed. 2001; 40: 387
• 11a Page JP, RajanBabu TV. J. Am. Chem. Soc. 2012; 134: 6556
• 11b Sharma RK, RajanBabu TV. J. Am. Chem. Soc. 2010; 132: 3295
• 11c Saha B, Smith CR, RajanBabu TV. J. Am. Chem. Soc. 2008; 130: 9000
• 11d Zhang A, RajanBabu TV. J. Am. Chem. Soc. 2006; 128: 54
• 11e RajanBabu TV. Chem. Rev. 2003; 103: 2845
• 12 McCammant MS, Liao L, Sigman MS. J. Am. Chem. Soc. 2013; 135: 4167
• 13a Patil NT, Yamamoto Y. Synlett 2007; 1994 ; and references cited therein
• 13b Nakamura H, Sekido M, Ito M, Yamamoto Y. J. Am. Chem. Soc. 1998; 120: 6838
• 13c Sekido M, Aoyagi K, Nakamura H, Kabuto C, Yamamoto Y. J. Org. Chem. 2001; 66: 7142
• 14 Yoshikawa E, Radhakrishnan KV, Yamamoto Y. Tetrahedron Lett. 2000; 41: 729
• 15a Lu S, Jin T, Bao M, Asiri AM, Yamamoto Y. Tetrahedron Lett. 2012; 53: 1210
• 15b Nakamura H, Shimizu K. Tetrahedron Lett. 2011; 52: 426
• 15c Lu S, Xu Z, Bao M, Yamamoto Y. Angew. Chem. Int. Ed. 2008; 47: 4366
• 15d Wallner OA, Szabo KJ. Org. Lett. 2002; 4: 1563
• 15e Pichierri F, Yamamoto Y. J. Org. Chem. 2007; 72: 861
• 15f Nakamura H, Shibata H, Yamamoto Y. Tetrahedron Lett. 2000; 41: 2911
• 15g Nakamura H, Ohtaka M, Yamamoto Y. Tetrahedron Lett. 2002; 43: 7631
• 15h Ohtaka M, Nakamura H, Yamamoto Y. Tetrahedron Lett. 2004; 45: 7339
• 15i Bao M, Nakamura H, Yamamoto Y. J. Am. Chem. Soc. 2001; 123: 759
• 15j Nakamura H, Asao N, Yamamoto Y. J. Chem. Soc., Chem. Commun. 1995; 1273
• 16 George SC, John J, Anas S, John J, Yamamoto Y, Suresh E, Radhakrishnan KV. Eur. J. Org. Chem. 2010; 5489
• 17 George SC, Thulasi S, Anas S, Radhakrishnan KV, Yamamoto Y. Org. Lett. 2011; 13: 4984
• 18 Sato Y, Oonishi Y, Mori M. J. Org. Chem. 2003; 68: 9858
• 19a Jaganmohan M, Shanmugasundaram M, Cheng C.-H. J. Org. Chem. 2004; 69: 4053
• 19b Jaganmohan M, Shanmugasundaram M, Cheng C.-H. Org. Lett. 2003; 5: 881
• 20 Nair V, Remadevi B, Vidya N, Menon RS, Abhilash N, Rath NP. Tetrahedron Lett. 2004; 45: 3203
• 21 Typical Procedure (Compound 4a): To a degassed solution of [PdCl₂(PPh₃)₂] (4.4 mg, 0.0064 mmol) in anhydrous THF (2 mL) in a Schlenk tube, allyltributyl-stannane 3 (85.2 mg, 0.25 mmol) was added followed by allyl chloride 2 (19.6 mg, 0.25 mmol). To this, 1a (42.02 mg, 0.12 mmol) was added (in THF) and the mixture was stirred at room temperature for 8 h. After the completion of the reaction (as evident by TLC), the solvent was removed under reduced pressure and the residue was purified by using silica gel (100–200 mesh) column chromatography (EtOAc–hexane, 12%) to afford 4a (41.1 mg, 78%).
• 22 Spectral Data of 4a: R_f = 0.46 (EtOAc–hexane, 4:6); IR (neat): 3079, 2955, 2919, 2850, 2313, 2246, 1734, 1604, 1510, 1461, 1376, 1290, 1248, 1177, 1118, 1032 cm^–1; ¹H NMR (500 MHz, CDCl₃): δ = 7.26–7.24 (m, 1 H), 7.08 (d, J = 8.5 Hz, 1 H), 6.98–6.94 (m, 2 H), 5.94–5.86 (m, 1 H), 5.56–5.47 (m, 1 H), 5.42–5.35 (m, 2 H), 5.05–4.98 (m, 2 H), 3.89 (s, 3 H), 3.84 (s, 3 H), 3.72 (s, 3 H), 3.18–3.15 (m, 1 H), 2.87–2.75 (m, 2 H), 2.63–2.58 (m, 1 H), 2.27–2.21 (m, 1 H); ¹³C NMR (125 MHz, CDCl₃): δ = 171.0, 166.0, 160.4, 137.4, 136.6, 134.0, 131.1, 130.1, 128.7, 126.0, 123.5, 118.1, 114.5, 114.3, 113.7 (2C), 55.3, 52.6, 52.5, 48.2, 42.7, 42.5, 33.8; HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₃H₂₄N₂NaO₅: 431.15829; found: 431.15646.
• 23 CCDC-933875.