Heck Reaction of 2-(Arylmethylene)cyclopropylcarbinols with Iodobenzene

Abstract

Palladium(0)-catalyzed Heck reaction of 2-(arylmethylene)cyclopropylcarbinols with iodobenzene produces the corresponding ring-opened 4,5-arylphenylpent-4-enals as the major products in moderate yields in the presence of KF in acetonitrile-water with 2,2′-bipyridine as a ligand.

Key words

2-(arylmethylene)cyclopropylcarbinols - iodobenzene - Heck reaction - ring-opening reaction - 2,2′-bipyridine

References and Notes

• For recent reviews on metal-catalyzed cross-coupling reactions:
• 1a Metal-catalyzed Cross-coupling Reactions   Diederich F. Stang PJ. Wiley; New York: 1998. 
• 1b Metal-catalyzed Cross-coupling Reactions   de Meijere A. Diederich F. Wiley; Weinheim: . 
• 1c Cross-coupling Reactions, A Practical Guide, In Top. Curr. Chem.   Vol. 219:  Miyaura N. Springer; Berlin: 2002. 
• 1d Handbook of Organopalladium Chemistry for Organic Synthesis   Vol. 1 and 2:  Negishi E. de Meijere A. Wiley; New York: 2002. 
• 1e Tsuji J. Palladium Reagents and Catalysts   Wiley; Chichester: 1995. 
• 1f Tsuji J. Palladium Reagents and Catalysts   Wiley; Chichester: 2004. 
• 2 For the synthesis of MCPs, see: Brandi A. Goti A. Chem. Rev.  1998,  98:  589 
• For recent reviews on MCPs, see:
• 3a Nakamura I. Yamamoto Y. Adv. Synth. Catal.  2002,  344:  111 
• 3b Brandi A. Cicchi S. Cordero FM. Goti A. Chem. Rev.  2003,  103:  1213 
• 3c Nakamura E. Yamago S. Acc. Chem. Res.  2002,  35:  867 
• Selected recent articles on MCPs, see:
• 4a Nakamura I. Oh BH. Saito S. Yamamoto Y. Angew. Chem. Int. Ed.  2001,  40:  1298 
• 4b Oh BH. Nakamura I. Saito S. Yamamoto Y. Tetrahedron Lett.  2001,  42:  6203 
• 4c Yamago S. Nakamura E. J. Org. Chem.  1990,  55:  5553 
• 4d Yamago S. Yanagawa M. Nakamura E. Chem. Lett.  1999,  879 
• 4e Camacho DH. Nakamura I. Saito S. Yamamoto Y. J. Org. Chem.  2001,  66:  270 
• 4f Nakamura I. Itagaki H. Yamamoto Y. J. Org. Chem.  1998,  63:  6458 
• 4g Yamago S. Yanagawa M. Nakamura E. Chem. Lett.  1999,  879 
• 4h Lautens M. Han W. Liu JH.-C. J. Am. Chem. Soc.  2003,  125:  4028 
• 4i Siriwardana AI. Kamada M. Nakamura I. Yamamoto Y. J. Org. Chem.  2005,  70:  5932 
• 4j Scott ME. Lautens M. Org. Lett.  2005,  7:  3045 
• 4k Scott ME. Han W. Lautens M. Org. Lett.  2004,  6:  3309 
• 4l Lautens M. Han W. J. Am. Chem. Soc.  2002,  124:  6312 
• 5a Shi M. Liu L.-P. Tang J. Org. Lett.  2005,  7:  3085 
• 5b Shi M. Liu L.-P. Tang J. J. Org. Chem.  2005,  70:  10420 
• 5c Liu L.-P. Shi M. Chem. Commun.  2004,  2878 
• For Heck reaction of MCPs with iodobenzene, see:
• 6a Bräse S. de Meijere A. Angew. Chem., Int. Ed. Engl.  1995,  34:  2545 ; and references cited therein
• 6b de Meijere A. Nüske H. Es-Sayed M. Labahn T. Schroen M. Bräse S. Angew. Chem. Int. Ed.  1999,  38:  3670 
• 6c For the synthesis of 2-(arylmethylene)cyclopropylcarbinols, see: Okuma K. Tanaka Y. Yoshihira K. Ezaki A. Koda G. Otha H. Hara K. Kashimura S. J. Org. Chem.  1993,  58:  5915 
• 6d Lautens M. Delanghe PHM. J. Org. Chem.  1993,  58:  5037 
• 6e Corre ML. Hercouet A. Bessieres B. J. Org. Chem.  1994,  59:  5483 
• 7a Patil NT. Kadota I. Shibuya A. Gyoung Y.-S. Yamamoto Y. Adv. Synth. Catal.  2004,  346:  800 
• 7b Shi M. Wang B.-Y. Huang J.-W. J. Org. Chem.  2005,  70:  5606 
• 9a Dieck A. Heck RF. J. Org. Chem.  1975,  40:  1083 
• 9b Kim JI. Patel BA. Heck RF. J. Org. Chem.  1981,  46:  1067 

8

General Procedure for the Heck Reaction of MCPOLs ( E ) -1 with Iodobenzene.
Under an argon atmosphere, the mixture of MCPOL (E)-1 (0.3 mmol), Pd(OAc)₂ (0.06 mmol), bipyridine (0.066 mmol), KF (0.9 mmol), iodobenzene (1.5 mmol), H₂O (0.6 mmol) and MeCN (3.0 mL) was stirred for 3-5 d at 80 °C. The solvent was removed under reduced pressure and the residue was purified by a silica gel column chromatography to give the product.
Representative Sample Data: 4,5-Diphenyl-pent-4-enal (2a). This compound was obtained as a colorless solid
(50 mg, 70%). ¹H NMR (300 MHz, CDCl₃, TMS): δ = 2.51 (td, J = 7.8, 1.8 Hz, 2 H, CH₂), 2.83 (t, J = 7.8 Hz, 2 H, CH₂), 6.49 (s, 1 H, CH), 6.89-6.92 (m, 2 H, ArH), 7.04-7.32 (m, 8 H, ArH), 9.73 (t, J = 1.8 Hz, 1 H, CHO). ¹³C NMR (75 MHz, CDCl₃, TMS): δ = 33.0, 42.1, 126.4, 127.19, 127.24, 127.8, 128.5, 128.7, 128.9, 136.7, 140.0, 140.8, 201.8. This is a known compound and its ¹H NMR and ¹³H NMR spectroscopic data are consistent with those reported, see: Dérien, S.; Jan, D.; Dixneuf, P. H. Tetrahedron 1996, 52, 5511.
4,5-Diphenyl-pent-2,4-dien-1-ol (3a). This compound was obtained as a colorless solid (7 mg, 9%). IR (KBr): 695, 756, 968, 1026, 1090, 1446, 1492, 1671, 2852, 2923, 3022, 3359cm^-1. ¹H NMR (300 MHz, CDCl₃, TMS): δ = 4.22 (d, J = 5.4 Hz, 2 H, CH₂OH), 5.44 (dt, J = 15.3, 5.4 Hz, 1 H, CHCH₂), 6.60 (s, 1 H, CH), 6.67 (d, J = 15.3 Hz, 1 H, CH), 6.86-7.41 (m, 10 H, ArH). MS (EI) m/z: 91 [(M - 145)⁺, 79.83], 115 [(M - 121)⁺, 100.0], 128 [(M - 108)⁺, 53.65], 174 [(M - 52)⁺, 52.62], 236 (M⁺, 9.93). HRMS (EI) calcd for C₁₇H₁₄ (C₁₇H₁₆O - H₂O): 218.1096; found: 218.1101.