Copper(II) Acetate Mediated Reactions of Methylenecyclopropane and Diphenyl Diselenide

Abstract

Phenylselenyl-substituted cyclobutenes and 1,3-butadienes were obtained from a copper(II) acetate mediated reaction between methylenecyclopropanes and diphenyl diselenide.

Key words

methylenecyclopropane - free radical - selenium - copper - electron transfer

References and Notes

• 1 For the preparation of the MCPs, see: Brandi A. Goti A. Chem. Rev.  1998,  98:  589 ; and references cited therein
• 2a Brandi A. Cicchi S. Cordero FM. Goti A. Chem. Rev.  2003,  103:  1213 
• 2b Nakamura I. Yamamoto Y. Adv. Synth. Catal.  2002,  344:  111 ; and references cited therein
• 3a Camacho DH. Nakamura I. Saito S. Yamamoto Y. J. Org. Chem.  2001,  66:  270 
• 3b Tsukada N. Shibuya A. Nakamura I. Yamamoto Y. J. Am. Chem. Soc.  1997,  119:  8123 
• 3c Nakamura I. Saito S. Yamamoto Y. J. Am. Chem. Soc.  2000,  122:  2661 
• 3d Nakamura I. Siriwardana AI. Saito S. Yamamoto Y. J. Org. Chem.  2002,  67:  3445 
• 3e Nakamura I. Itagaki H. Yamamoto Y. J. Org. Chem.  1998,  63:  6458 
• 3f Nakamura I. Oh BH. Saito S. Yamamoto Y. Angew. Chem. Int. Ed.  2001,  40:  1298 
• 3g Lautens M. Ren Y. Delanghe PHM. J. Am. Chem. Soc.  1994,  116:  8821 
• 3h Lautens M. Ren Y. J. Am. Chem. Soc.  1996,  118:  9597 
• 3i Lautens M. Ren Y. J. Am. Chem. Soc.  1996,  118:  10668 
• 3j Suginome M. Matsuda T. Ito Y. J. Am. Chem. Soc.  2000,  122:  11015 
• 3k Lautens M. Meyer C. Lorenz A. J. Am. Chem. Soc.  1996,  118:  10676 
• 3l Bessmertnykh AG. Blinov KA. Grishin YK. Donskaya NA. Tveritinova EV. Yur"eva NM. Beletskaya IP. J. Org. Chem.  1997,  62:  6069 
• 4a Shi M. Xu B. Tetrahedron Lett.  2003,  44:  3839 
• 4b Huang J. Shi M. Tetrahedron Lett.  2003,  44:  9343 
• 4c Shao L. Shi M. Eur. J. Org. Chem.  2004,  426 
• 4d Shi M. Xu B. Org. Lett.  2002,  4:  2145 
• 4e Shi M. Chen Y. Xu B. Tang J. Tetrahedron Lett.  2002,  43:  8019 
• 4f Shi M. Shao L. Xu B. Org. Lett.  2003,  5:  579 
• 4g Xu B. Shi M. Org. Lett.  2003,  5:  1415 
• 5a Xu B. Chen Y. Shi M. Tetrahedron Lett.  2002,  43:  2781 
• 5b Zhou H. Huang X. Chen W. J. Org. Chem.  2004,  69:  5471 
• 5c Liu L. Shi M. Chem. Commun.  2004,  2878 
• 5d Huang X. Yu L. Synlett  2005,  2953 
• 5e Huang J. Shi M. J. Org. Chem.  2005,  70:  3859 
• 5f Yu L. Huang X. Xie M. Synlett  2006,  423 
• 5g Yu L. Huang X. Synlett  2006,  2136 
• 6a Kochi JK. J. Am. Chem. Soc.  1963,  85:  1958 
• 6b Kochi JK. Bemis A. J. Am. Chem. Soc.  1968,  90:  4038 
• 6c Kochi JK. Bemis A. Jenkins CL. J. Am. Chem. Soc.  1968,  90:  4616 
• 6d Kochi JK. Free Radicals   Vol. I:  Wiley; New York: 1968.  p.591 
• For selected recent articles about cyclobutenes, see:
• 7a Delas C. Urabe H. Sato F. J. Am. Chem. Soc.  2001,  123:  7937 
• 7b Tantillo DJ. Hoffmann R. J. Am. Chem. Soc.  2001,  123:  9855 
• 7c Winkler JD. McLaughlin EC. Org. Lett.  2005,  7:  227 
• 7d Murakami M. Usui I. Hasegawa M. Matsuda T. J. Am. Chem. Soc.  2005,  127:  1366 
• 7e Inanaga K. Takasu K. Ihara M. J. Am. Chem. Soc.  2005,  127:  3668 
• 8a Back TG. Organoselenium Chemistry: A Practical Approach   Oxford; UK: 1999. 
• 8b Zeni G. Stracke MP. Nogueira CW. Braga AL. Menezes PH. Stefani HA. Org. Lett.  2004,  6:  1135 
• 8c Prediger P. Moro AV. Nogueira CW. Savegnago L. Menezes PH. Rocha JBT. Zeni G. J. Org. Chem.  2006,  71:  3786 
• 8d Soares do Rego Barros O. Nogueira CW. Stangherlin EC. Menezes PH. Zeni G. J. Org. Chem.  2006,  71:  1552 
• 8e Shafiee A. Mazloumi A. Cohen VI. J. Heterocycl. Chem.  1979,  16:  1563 
• 8f Shafiee A. Shafaati A. Khamench BH. J. Heterocycl. Chem.  1989,  26:  709 
• 9a Murakami M. Usui I. Hasegawa M. Matsuda T. J. Am. Chem. Soc.  2005,  127:  1366 
• 9b Shi M. Wang B. Li J. Eur. J. Org. Chem.  2005,  759 
• 11 Liu L. Shi M. J. Org. Chem.  2004,  69:  2805 
• For selected recent articles about buta-1,3-dienes, see:
• 13a Shi M. Wang B. Huang J. J. Org. Chem.  2005,  70:  5606 
• 13b Wong K. Hung Y. Tetrahedron Lett.  2003,  44:  8033 
• 13c Taylor DK. Avery TD. Greatrex BW. Tiekink ERT. Macreadie IG. Macreadie PI. Humphries AD. Kalkanidis M. Fox EN. Klonis N. Tilley L. J. Med. Chem.  2004,  47:  1833 

10

2-Phenylselenyl-3,3-diarylcyclobutene (6), typical procedure: Under an N₂ atmosphere, a solution of diphenylmethylenecyclopropane (1a, 0.062 g, 0.3 mmol), diphenyl diselenide (0.094 g, 0.3 mmol) and Cu(OAc)₂ (0.060 g, 0.3 mmol) in AcOH (2 mL) was irradiated with a tungsten lamp (300 W). The temperature rose to 40 °C because of the irradiation. The reaction was monitored by TLC (PE). When the reaction was complete, the solvent was evaporated under vacuum and the residue was subjected to preparative TLC (PE) to afford 6a in 65% yield. IR (KBr): 3055, 1575, 1491, 1217, 1025, 750, 696 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 7.22-7.60 (m, 15 H), 6.12 (t, J = 0.8 Hz, 1 H), 3.17 (d, J = 0.8 Hz, 2 H); ¹³C NMR (100 MHz, CDCl₃): δ = 46.9, 61.9, 126.4, 127.4, 127.5, 128.0, 128.1, 129.3, 133.9, 134.8, 141.8, 144.1; MS (EI, 70 eV): m/z (%) = 362 (12) [M⁺], 281 (14), 205 (100); HRMS (EI): m/z calcd for C₂₂H₁₈Se: 362.0574; found: 362.0574.

12

1,1-Diaryl-2-phenylselenylbuta-1,3-diene (11), typical procedure: Under an N₂ atmosphere, a solution of diphenylmethylenecyclopropane (1a, 0.062 g, 0.3 mmol), diphenyl diselenide (0.094 g, 0.3 mmol) and Cu(OAc)₂ (0.060 g, 0.3 mmol) in AcOH (0.2 mL) acid was stirred at 110 °C. The reaction was monitored by TLC (PE). When the reaction was complete, the solvent was evaporated under vacuum and the residue was subjected to preparative TLC (PE) to afford 11a in 68% yield. IR (film): 3054, 1576, 1477, 1440, 737, 697 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 7.14-7.34 (m, 15 H), 6.56-6.63 (m, 1 H), 5.81-5.85 (m, 1 H), 5.22-5.25 (m, 1 H); ¹³C NMR (100 MHz, CDCl₃): δ = 120.9, 125.8, 127.3, 127.7, 128.1, 128.9, 129.4, 130.0, 130.1, 130.2, 133.0, 135.4, 141.6, 144.1, 151.6; MS (EI, 70 eV): m/z (%) = 362 (30) [M⁺], 281 (15), 205 (100); HRMS (EI): m/z calcd for C₂₂H₁₈Se: 362.0574; found: 362.0567.