Abstract
Background: Organoselenides are important building blocks of several biologically important molecules and natural products. Several protocols have been developed by chemists for their synthesis. Transition metal-catalyzed cross-coupling is a powerful tool for this purpose in the last two decades. Various transition metal catalysts e.g. Pd, Ni, Cu, In etc. have been used for performing C-Se cross-coupling in the presence or absence of ligands.
Objective: Development of a sustainable protocol for transition metal-catalyzed C-Se cross-coupling is the main objective of this research. Recently, Cobalt has been applied as a cheap and sustainable transition metal catalyst in several organic reactions. This protocol is focused on applying cobalt salt as a catalyst for performing C-Se cross-coupling for the first time.
Methods: Co(acac)2 has been successfully employed for performing Se-arylations in the presence of CuI, which acts as a co-catalyst under microwave irradiation. NMP was used as solvent and KOH as a reductant in this reaction.
Results: Both iodo-and bromoarenes have been used to perform C-Se cross-coupling with diaryl diselenide under this Co/Cu dual catalytic system. The reaction was successful with both electrondonating and withdrawing groups in ortho-, meta-, and para-positions in the aromatic ring of Bromo and iodoarenes.
Conclusion: This is an effective protocol for the preparation of organoselenides, catalyzed by cobalt in the presence of copper. The mechanism has been established by several experimental techniques.
Keywords: Cobalt, copper, cross-coupling, organoselenides, green chemistry, dual catalysis.
Graphical Abstract
[http://dx.doi.org/10.1021/cr000426w] [PMID: 11710243]
[http://dx.doi.org/10.1021/cr0406559] [PMID: 15584701]
[http://dx.doi.org/10.1126/science.179.4073.588] [PMID: 4686466]
[http://dx.doi.org/10.1016/S0022-328X(00)00265-5]
(b)Zhao, H.; Hao, W.; Xi, Z.; Cai, M. Palladium-catalyzed crosscoupling of PhSeSnBu3 with aryl and alkyl halides in ionic liquids: a practical synthetic method of diorganyl selenides. New J. Chem, 2011, 35, 2661-2665.
[http://dx.doi.org/10.1039/c1nj20514e]
(c)Senol, E.; Scattolin, T.; Schoenebeck, F. selenolation of aryl iodides and bromides enabled by a bench-stable PdI dimer Chemistry, 2019, 25(40), 9419-9422.
[http://dx.doi.org/10.1002/chem.201900951] [PMID: 30913326]
(d)Grenader, K.; Schüpbach, B.; Peters, A.; Kümmel, O.; Halter, O.; Terfort, A. Catalytic C-Se bond formation under very mild conditions for the two-step, one-pot synthesis of aryl selenoacetates Adv. Synth. Catal, 2012, 354, 2653.
[http://dx.doi.org/10.1002/adsc.201200486]
(e)Bonaterra, M.; Rossi, R.A.; Martín, S.E. Organoheteroatom stannanes in palladium-catalyzed cross-coupling reactions with 1- Naphthyl Triflate Organometallics, 2009, 28, 933-936.
[http://dx.doi.org/10.1021/om8009816]
(f)Bonaterra, M.; Martín, S.E.; Rossi, R.A. Palladium-catalyzed phenyl-selenylation with n-Bu3SnSePh in one-pot two-step reactions Tetrahedron Lett, 2006, 47, 3511-3515.
[http://dx.doi.org/10.1016/j.tetlet.2006.03.106]
(g)Wallner, O.A.; Szabó, K.J. Employment of palladium pincer-complexes in phenylselenylation of organohalides. J. Org. Chem., 2005, 70(23), 9215-9221.
[http://dx.doi.org/10.1021/jo051266x] [PMID: 16268593]
[http://dx.doi.org/10.1002/adsc.200900095]
[http://dx.doi.org/10.1021/om00123a007]
(b)Li, Y.; Wang, H.; Li, X.; Chen, T.; Zhao, D. CuS/Fe: a novel and highly efficient catalyst system for coupling reaction of aryl halides with diaryl diselenides Tetrahedron, 2010, 66, 8583-8586.
[http://dx.doi.org/10.1016/j.tet.2010.09.061]
(c)Wang, L.; Wang, M.; Huang, F. A simple copper salt-catalyzed synthesis of unsymmetrical diaryl selenides and tellurides from arylboronic acids with diphenyl diselenide and ditelluride. Synlett, 2005, 2007-2010.
(d)Singh, D.; Alberto, E.E.; Rodrigues, O.E.D.; Braga, A.L. Eco-friendly cross-coupling of diaryl diselenides with aryl and alkyl bromides catalyzed by CuO nanopowder in ionic liquid. Green Chem, 2009, 11, 1521-1524.
[http://dx.doi.org/10.1039/b916266f]
(e)Chatterjee, T.; Ranu, B.C. Solvent-controlled halo-selective selenylation of aryl halides catalyzed by Cu(II) supported on Al2O3. A general protocol for the synthesis of unsymmetrical organo mono- and bis-selenides. J. Org. Chem., 2013, 78(14), 7145-7153.
[http://dx.doi.org/10.1021/jo401062k] [PMID: 23786642]
[http://dx.doi.org/10.1039/C2RA22415A]
(b)Didehban, K.; Vessally, E.; Hosseinian, A.; Edjlali, E.; Khosroshahi, E.S. Nano catalysts for C-Se crosscoupling reactions RSC Advances, 2018, 8, 291-301.
[http://dx.doi.org/10.1039/C7RA12663H]
(c)Swapna, K.; Murthy, S.N.; Durga Negeswar, Y.V. Magnetically separable and reusable copper ferrite nanoparticles for cross-coupling of aryl halides with diphenyl diselenide. Eur. J. Org. Chem., 2011, 10, 1940-1946.
[http://dx.doi.org/10.1002/ejoc.201001639]
[http://dx.doi.org/10.1021/ol062344l] [PMID: 17107085]
[http://dx.doi.org/10.1039/c1ra00406a]
[http://dx.doi.org/10.1002/chem.200802483] [PMID: 19219864]
[http://dx.doi.org/10.1039/C0OB00454E] [PMID: 21186392]
[http://dx.doi.org/10.1002/chem.201500058] [PMID: 25926040]
[http://dx.doi.org/10.1039/C6NJ02247B]
[http://dx.doi.org/10.1039/C8OB00743H] [PMID: 29737996]
[http://dx.doi.org/10.1021/om300586p] [PMID: 23204631]
[http://dx.doi.org/10.1039/DT9830002561]
(b)Kundu, D.; Maity, P.; Ranu, B.C. Copper-assisted nickel catalyzed ligand-free C(sp2)-O cross-coupling of vinyl halides and phenols. Org. Lett., 2014, 16(4), 1040-1043.
[http://dx.doi.org/10.1021/ol500134p] [PMID: 24502267]
[http://dx.doi.org/10.1021/jo402071b] [PMID: 24116379]