Nano Copper Oxide Catalyzed Synthesis of Symmetrical Diaryl Selenides via Cascade Reaction of KSeCN with Aryl Halides

Abstract

An unprecedented transfer of selenium ion from potassium selenocyanate was observed in C-Se cross-coupling reaction catalyzed by copper oxide nanoparticles under ligand-free conditions. Utilizing this protocol wide range of symmetrical diaryl selenides were obtained in excellent yields. Nano-CuO is recyclable up to four cycles without loss of catalytic activity.

Key words

aryl halides - potassium selenocyanate - cross-coupling - nano copper oxide - ligand-free conditions - recyclable

References and Notes

• 1a Sarma BK. Mugesh G. Org. Biomol. Chem.  2008,  6:  965 
• 1b Nogueira CW. Zeni G. Rocha JB. Chem. Rev.  2004,  104:  6255 
• 1c Mugesh G. du Mont WW. Sies H. Chem. Rev.  2001,  101:  2125 
• 1d Mugesh G. Singh HB. Chem. Soc. Rev.  2000,  29:  347 
• 2a Krief A. Hevesi L. Organoselenium Chemistry I   Springer; Berlin: 1988. 
• 2b Comasseto JV. Ling LW. Petragnani N. Stefani HA. Synthesis  1997,  373 
• 2c Organoselenium Chemistry: A Practical Approach   Back TG. Oxford University Press; Oxford: 1999. 
• 2d Procter DJ. J. Chem. Soc., Perkin Trans. 1  2000,  835 
• 3a Braga AL. Ludtke DS. Vargas F. Braga RC. Synlett  2006,  1453 
• 3b Braga AL. Vargas F. Sehnem JA. Braga RC. J. Org. Chem.  2005,  70:  9021 
• 3c Braga AL. Paixao MW. Ludtke DS. Silveira CC. Rodrigues OED. Org. Lett.  2003,  5:  3635 
• 3d Braga AL. Silva SJN. Ludtke DS. Drekener RL. Silveira CC. Rocha JBT. Wessjohann LA. Tetrahedron Lett.  2002,  43:  7329 
• 3e Braga AL. Paixao MW. Marin G. Synlett  2005,  1975 
• 3f Braga AL. Ludtke DS. Sehnem JA. Alberto EE. Tetrahedron  2005,  61:  11664 
• 4 Engman L. Cotgreave I. Angulo M. Taylor CW. Paine-Murrieta GD. Powis G. Anticancer Res.  1997,  17:  4599 
• 5a Back TG. Moussa Z. J. Am. Chem. Soc.  2003,  125:  13455 
• 5b Nogueira CW. Zeni G. Rocha JBT. Chem. Rev.  2004,  104:  6255 
• 5c Anderson C.-M. Allberg A. Hogberg T. Adv. Drug. Res.  1996,  28:  65 
• 5d Clark LC. Combs GF. Turnbull BW. Slate EH. Chalker DK. Chow J. Davis LS. Glover RA. Graham GF. Gross EG. Krongrad A. Lesher JL. Park K. Sanders BB. Smith CL. Taylor R. J. Am. Med. Assoc.  1996,  276:  1957 
• 5e Woods JA. Hadfield JA. McGown AT. Fox BW. Org. Biomol. Chem.  1993,  1:  333 
• 6a Suzuki H. Abe H. Osuka A. Chem. Lett.  1981,  151 
• 6b Osuka A. Ohmasa N. Suzuki H. Synth. Commun.  1982,  857 
• 6c Andersson CM. Hallberg A. Linden M. Brattsand R. Moldeus P. Cotgreave I. Free Radical Biol. Med.  1994,  16:  17 
• 6d Andersson CM. Hallberg A. Hugberg T. Adv. Drug Res.  1996,  28:  65 
• 7a Nishiyama Y. Tokunaga K. Sonoda N. Org. Lett.  1999,  1:  1725 
• 7b Beletskaya IP. Sigeev AS. Peregudov AS. Petrovskii PV. J. Organomet. Chem.  2000,  96:  605 
• 8 Cristau HJ. Chabaud B. Labaudiniere R. Christol H. Organometallics  1985,  4:  657 
• 9a Bhadra S. Saha A. Ranu BC. J. Org. Chem.  2010,  75:  4864 
• 9b Singh D. Alberto EE. Rodrigues OED. Braga AL. Green Chem.  2009,  11:  1521 
• 9c Alves D. Santos CG. Paixao MW. Soares LC. de Souza D. Rodrigues OED. Braga AL. Tetrahedron Lett.  2009,  50:  6635 
• 9d Saha A. Saha D. Ranu BC. Org. Biomol. Chem.  2009,  7:  1652 
• 9e Taniguchi N. Onami T. J. Org. Chem.  2004,  69:  915 
• 9f Kumar S. Engman L. J. Org. Chem.  2006,  71:  5400 
• 9g Taniguchi N. J. Org. Chem.  2007,  72:  1241 
• 9h Gujadhur RK. Venkataraman D. Tetrahedron Lett.  2003,  44:  81 
• 9i Beletskaya IP. Sigeev AS. Peregudov AS. Petrovskii PV. Tetrahedron Lett.  2003,  44:  7039 
• 9j Wang L. Wang M. Huang F. Synlett  2005,  2007 
• 9k Chang D. Bao W. Synlett  2006,  1786 
• 9l Taniguchi N. Onami T. Synlett  2003,  829 
• 9m Taniguchi N. Synlett  2005,  1687 
• 10 Wang M. Ren K. Wang L. Adv. Synth. Catal.  2009,  351:  1586 
• 11 Ren K. Wang M. Wang L. Org. Biomol. Chem.  2009,  7:  4858 
• 12 Murthy SN. Madhav B. Reddy VP. Nageswar YVD. Eur. J. Org. Chem.  2009,  5902 
• 13 Reddy VP. Kumar AV. Rao KR. J. Org. Chem.  2010,  75:  8720 
• 14a Swapna K. Murthy SN. Nageswar YVD. Eur. J. Org. Chem.  2010,  6678 
• 14b Reddy VP. Swapna K. Kumar AV. Rao KR. J. Org. Chem.  2009,  74:  3189 
• 14c Swapna K. Kumar AV. Reddy VP. Rao KR.
  J. Org. Chem.  2009,  74:  7514 
• 14d Reddy VP. Kumar AV. Swapna K. Rao KR. Org. Lett.  2009,  11:  951 
• 14e Reddy VP. Kumar AV. Swapna K. Rao KR. Org. Lett.  2009,  11:  1697 
• 14f Reddy VP. Kumar AV. Swapna K. Rao KR. Synlett  2009,  2783 
• 14g Reddy VP. Kumar AV. Rao KR. Chem. Lett.  2010,  39:  212 
• 14h Reddy VP. Kumar AV. Rao KR. Tetrahedron Lett.  2010,  51:  3181 
• 15a Pacchioni G. Surf. Rev. Lett.  2000,  7:  277 
• 15b Knight WD. Clemenger K. de Heer WA. Saunders WAM. Chou Y. Cohen ML. Phys. Rev. Lett.  1984,  52:  2141 
• 15c Kaldor A. Cox D. Zakin MR. Adv. Chem. Phys.  1988,  70:  211 
• 16a Yavuz S. Diºli A. Yildirir Y. Türker L. Molecules  2005,  10:  1000 
• 16b Krief A. Delmotte C. Dumont W. Tetrahedron  1997,  53:  12147 

17

General Procedure for the Synthesis of Diaryl Selenides
To a stirred solution of aryl halides (2.0 mmol) and potassium selenocyanate (1.2 equiv) in dry DMSO (2.0 mL) at r.t. was added nano-CuO (5.0 mol%) followed by KOH (2.0 equiv) and heated at 110 ˚C for 15 h. The progress of the reaction was monitored by TLC. After the reaction was complete, the reaction mixture was allowed to cool, and a 1:1 mixture of EtOAc-H₂O (20 mL) was added. The combined organic extracts were washed with brine and H₂O and dried with anhyd Na₂SO₄. The solvent and volatiles were completely removed under vacuum to give the crude product, which was purified by column chromatography on silica gel (PE-EtOAc) to afford the corresponding coupling product in excellent yields.
Recycling of the Catalyst After the reaction was complete, the reaction mixture was allowed to cool, a 1:1 mixture of EtOAc- H₂O (2.0 mL) was added, and CuO was removed by centrifugation. After each cycle, the catalyst was recovered by simple centrifugation, washing with deionized H₂O and EtOAc and then drying in vacuo. The recovered nano-CuO was used directly in the next cycle. Dinaphthalen-1-ylselane (Table 2, Entry 11) Yellow liquid. IR (neat): ν = 3091, 2928, 1588, 1390, 1077, 968, 848 cm^-¹. ^¹H NMR (200 MHz, CDCl₃, TMS): δ = 8.05-8.02 (m, 4 H), 7.79-7.65 (m, 4 H), 7.55-7.40 (m, 4 H), 7.15 (t, 2 H, J = 7.93Hz). ^¹³C NMR (50 MHz, CDCl₃, TMS): δ = 137.2, 133.9, 131.9, 128.8, 128.3, 127.5, 126.6, 125.6. ESI-MS: m/z = 335 [M + 1]. Anal. Calcd for C₂₀H₁₄Se(334): C, 72.07; H, 4.23. Found: C, 72.01; H, 4.18.
Bis[4-(benzyloxy)phenyl]selane (Table 2, Entry 13) Colorless oil. IR (neat): ν = 3099, 2923, 1598, 1397, 1081, 961, 842 cm^-¹. ^¹H NMR (200 MHz, CDCl₃, TMS): δ = 7.51 (d, 4 H, J = 9.16 Hz), 7.39-7.25 (m, 10 H), 6.70 (d, 4H, J = 9.16 Hz), 5.02 (s, 4 H). ^¹³C NMR (50 MHz, CDCl₃, TMS): δ = 158.63, 138.35, 136.35, 128.52, 128.11, 127.30, 117.53, 69.87. ESI-MS: m/z = 447 [M + 1]. Anal. Calcd for C₂₆H₂₂O₂Se(446): C, 70.11; H, 4.98. Found: C, 70.04; H, 4.91.
Dipyridin-3-ylselane (Table 2, Entry 18) ^¹H NMR (200 MHz, CDCl₃): δ = 8.69 (s, 2 H), 8.58-8.52 (m, 2 H), 7.73 (d, 2 H, J = 7.93 Hz), 7.25-7.19 (m, 2 H). ^¹³C NMR (50 MHz, CDCl₃, TMS): δ = 153.3, 148.9, 140.6, 124.4. ESI-MS: m/z = 237 [M + 1]. Anal. Calcd for C₁₀H₈N₂Se(236): C, 51.08; H, 3.43; N, 11.91. Found: C, 51.14; H, 3.46; N, 11.95. Dipyrimidin-5-ylselane (Table 2, Entry 20) Colorless oil. IR (neat): ν = 3092, 2960, 1597, 1444, 1068, 865, 738 cm^-¹. ^¹H NMR (200 MHz, CDCl₃, TMS): δ = 7.51 (s, 2 H), 7.25 (s, 4 H). ^¹³C NMR (50 MHz, CDCl₃, TMS):
δ = 132.9, 129.0, 127.5. ESI-MS: m/z = 239 [M + 1]. Anal. Calcd for C₈H₆N₄Se(238): C, 40.52; H, 2.55; N, 23.63. Found: C, 40.46; H, 2.45; N, 23.57.