Room-Temperature Palladium-Catalyzed Allyl Cross-Coupling Reaction with Boronic Acids Using Phosphine-Free Hydrazone Ligands

Abstract

Palladium-catalyzed allyl cross-coupling reaction of allylic acetates with a variety of boronic acids at room temperature using a catalytic amount of Pd(OAc)₂ with phosphine-free hydrazone as a ligand gave the allylbenzene derivatives in good yields.

Key words

palladium - catalysis - allyl cross-coupling - boronic ­acid - hydrazones

References and Notes

• For reviews, see the following:
• 1a Larhed M. Hallberg A. In Handbook of Organopalladium Chemistry for Organic Synthesis   Vol. 1:  Negishi E. Wiley-Interscience; New York: 2002.  p.1133 
• 1b Whitcombe NJ. Hii KK. Gibson SE. Tetrahedron  2001,  57:  7449 
• 1c Beletskaya IP. Cheprakov AV. Chem. Rev.  2000,  100:  3009 
• 1d Hegedus LS. Transition Metals in the Synthesis of Complex Organic Molecules   2nd ed.:  University Science Books; Sausalito CA: 1999.  Chap. 4.6.
• 1e Bräse S. de Meijere A. In Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim Germany: 1998.  Chap. 3.
• 1f Link JT. Overman LE. In Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim Germany: 1998.  Chap. 6.
• 1g Beller M. Riermeier TH. Stark G. In Transition Metals for Organic Synthesis   Vol. 1:  Beller M. Bolm C. Wiley-VCH; Weinheim Germany: 1998.  p.208 
• 1h Crisp GT. Chem. Soc. Rev.  1998,  27:  427 
• 1i Tsuji J. Palladium Reagents and Catalysts: Innovations in Organic Synthesis   Wiley; Chichester U.K.: 1995. 
• For reviews, see:
• 2a Llord-Williams P. Giralt E. Chem. Soc. Rev.  2001,  30:  145 
• 2b Suzuki A. J. Organomet. Chem.  1999,  576:  147 
• 2c Suzuki A. Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998.  p.49 
• 2d Stanforth SP. Tetrahedron  1998,  54:  263 
• 2e Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
• 3a Su C.-R. Shen Y.-C. Kuo P.-C. Leu Y.-L. Damu AG. Wang Y.-H. Wu T.-S. Bioorg. Med. Chem. Lett.  2006,  16:  6155 
• 3b Belley M. Chan CC. Gareau Y. Gallant M. Juteau H. Houde K. Lachance N. Labelle M. Sawyer N. Tremblay N. Limontage S. Carrière M.-C. Denis D. Greig GM. Slipez D. Gordon R. Chauret N. Lo C. Zamboni RJ. Metters KM. Bioorg. Med. Chem. Lett.  2006,  16:  5639 
• 3c Anderson JC. Headly C. Stapleton PD. Taylor PW. Tetrahedron  2005,  61:  7703 
• 3d Kramer B. Waldvugel SR. Angew. Chem. Int. Ed.  2004,  43:  2446 
• 4a Bouyssi D. Gerusz V. Balme G. Eur. J. Org. Chem.  2002,  2445 
• 4b Ortar G. Tetrahedron Lett.  2003,  44:  4311 
• 5 Uozumi Y. Danjo H. Hayashi T. J. Org. Chem.  1999,  64:  3384 
• 6 Polackova V. Toma S. Kappe CO. Tetrahedron  2007,  63:  8742 
• 7a Nájera C. Gil-Moltó J. Karlström S. Adv. Synth. Catal.  2004,  346:  1798 
• 7b Botella L. Nájera C.
  J. Organomet. Chem.  2002,  663:  46 
• 8a Mino T. Shirae Y. Sakamoto M. Fujita T. Synlett  2003,  882 
• 8b Mino T. Shirae Y. Sakamoto M. Fujita T. J. Org. Chem.  2005,  70:  2191 
• 9 Mino T. Shirae Y. Sasai Y. Sakamoto M. Fujita T. J. Org. Chem.  2006,  71:  6834 
• 10 Mino T. Shirae Y. Saito T. Sakamoto M. Fujita T.
  J. Org. Chem.  2006,  71:  9499 
• 11 Lawrence NJ. Muhammad F. Tetrahedron  1998,  54:  15345 
• 12a Llobet A. Masllorens E. Rodriguez M. Roglans A. Benet-Buchhollz J. Eur. J. Inorg. Chem.  2004,  8:  1601 
• 12b Rodríguez D. Sestelo PS. Sarandeses LA. J. Org. Chem.  2003,  68:  2518 
• 14a Durand S. Parrain J.-L. Santelli M. J. Chem. Soc., Perkin Trans. 1  2000,  253 
• 14b Andrey O. Glanzmann C. Landais Y. Parra-Rapado L. Tetrahedron  1997,  53:  2835 
• 14c Nicolaou KC. Ramphal JY. Petasis NA. Serhan CN. Angew. Chem., Int. Ed. Engl.  1991,  30:  1100 
• 15a Basavaiah D. Sharada DS. Kumaragurubaran N. Reddy RM. J. Org. Chem.  2002,  67:  7135 
• 15b Tsukada N. Sato T. Inoue Y. Chem. Commun.  2001,  237 
• 15c Klaps E. Schmid W. J. Org. Chem.  1999,  64:  7537 
• 15d Hara R. Nishihara Y. Landre PD. Takahashi T. Tetrahedron Lett.  1997,  38:  447 
• 15e Prasad ASB. Knochel P. Tetrahedron  1997,  53:  16711 
• 15f Denmark SE. Guagnano V. Dixon JA. J. Org. Chem.  1997,  62:  4610 
• 15g Matsuhashi H. Hatanaka Y. Kuroboshi M. Hiyama T. Tetrahedron Lett.  1995,  36:  1539 
• 15h Kobayashi Y. Ikeda E. Chem. Commun.  1994,  1789 
• 15i Matsushita H. Negishi E. J. Am. Chem. Soc.  1981,  103:  2882 
• 16 Kabalka GW. Al-Masum M. Org. Lett.  2006,  8:  11 
• 19 Keinan E. Kumar S. Dangur V. Vaya J. J. Am. Chem. Soc.  1994,  116:  11151 

13

General Procedure for Allyl Cross-Coupling Reaction of Cinnamyl and Allyl Acetate with Boronic Acids (Table 2): To a mixture of acetate (0.5 mmol), K₂CO₃ (138.2 mg, 1.0 mmol), Pd(OAc)₂ (2.24 mg, 0.01 mmol), and ligand 1c (2.22 mg, 0.01 mmol) in DMF (1.5 mL) and H₂O (0.5 mL) was added boronic acid (0.6 mmol) at r.t. under an atmosphere of argon. After 1 h, the mixture was diluted with EtOAc and H₂O. The organic layer was washed with brine, dried over MgSO₄, and concentrated under reduced pressure. The residue was purified by silica gel chromatography. All prepared compounds 3 (except for 3e) were known and identified by ^¹H NMR, ^¹³C NMR, and MS. Analytical Data of 3e (Table 2, entry 7): colorless oil. IR (neat): 1604 cm^-¹. ^¹H NMR (CDCl₃): δ = 2.29 (s, 6 H), 3.47 (d, J = 6.5 Hz, 2 H), 6.33 (dt, J = 15.7, 6.6 Hz, 1 H), 6.45 (d, J = 15.9 Hz, 1 H), 6.86 (s, 3 H), 7.16-7.37 (m, 5 H). ^¹³C NMR (CDCl₃):
δ = 21.1, 39.2, 126.1, 126.4, 127.0, 127.8, 128.5, 129.4, 130.8, 137.5, 138.0, 140.0. MS (EI, relative intensity): m/z = 222 (86) [M⁺]. HRMS (FAB-MS): m/z calcd for C₁₇H₁₈: 222.1409; found: 222.1408. GC-MS purity: 98.5%.

17

Preparation of Hydrazone 2b: To a solution of N-aminopiperidine (0.060 g, 0.60 mmol) in MeOH (2.0 mL) was added 2-pyridinecarboxaldehyde (0.054 g, 0.51 mmol) and the mixture was stirred for 24 h at r.t. The mixture was directly concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane-EtOAc, 4:1). Yield: 0.092 g, 0.49 mmol, 96%; colorless oil. IR (neat): 1572 cm^-¹. ^¹H NMR (CDCl₃): δ = 1.51-1.59 (m, 2 H), 1.66-1.79 (m, 4 H), 3.24 (t, J = 5.6 Hz, 4 H), 7.08-7.12 (m, 1 H), 7.59-7.64 (m, 2 H), 7.83 (dd, J = 8.1, 0.8 Hz, 1 H), 8.50 (dd, J = 4.8, 0.8 Hz, 1 H). ^¹³C NMR (CDCl₃): δ = 24.4, 25.4, 52.0, 119.4, 122.3, 134.3, 136.5, 149.4, 156.3. MS (EI, relative intensity): m/z = 189 (11) [M⁺]. HRMS (FAB-MS): m/z calcd for C₁₁H₁₅N₃: 189.1266; found: 189.1280.

18

General Procedure for Allyl Cross-Coupling Reaction of Disubstituted Allylic Acetates with 1-Naphthalene- boronic Acid (Table 3): To a mixture of acetate (0.5 mmol), Cs₂CO₃ (423.6 mg, 1.3 mmol), Pd(OAc)₂ (5.61 mg, 0.025 mmol), and ligand 2a (5.08 mg, 0.025 mmol) in MeCN (2 mL) was added 1-naphthaleneboronic acid (103.2 mg, 0.6 mmol) at r.t. under an atmosphere of argon. After 24 h, the mixture was diluted with EtOAc and H₂O. The organic layer was washed with brine, dried over MgSO₄, and concentrated under reduced pressure. The residue was purified by silica gel chromatography. Compounds 3m and 3n were known and identified by ^¹H NMR, ^¹³C NMR, and MS.