Nermin BİRİCİK, Nermin MERİÇ, Cezmi KAYAN, Zeynep ÖZGEN, Sevil Şeker AZİZOĞLU, Bahattin GÜMGÜM

Synthesis of new thiol-derivatized aminophosphines and their catalytic activities in C--C coupling reactions

A series of new aminophosphines [Ph$_{2}$PHN-C$_{6}$H$_{4}$-R, where R = $o$-SH (\textbf{4a}), $m$-SH (\textbf{4b) or }$p$-SH (\textbf{4c})] were readily synthesized from cheap starting materials by the phosphorylation reaction of $o$, $m$, and $p$-aminothiophenols with Ph$_{2}$PCl in the presence of triethyl amine. The new compounds were characterized by NMR and IR spectroscopy and microanalysis. In addition, aminophosphine ligands--palladium systems were investigated as precatalysts in C--C coupling reactions. Compounds \textbf{4b} and \textbf{4c }were proved to be excellent catalysts for Suzuki and Heck cross-coupling reactions.

Anahtar Kelimeler:

Aminophosphine, synthesis, catalysis, palladium, Suzuki--Heck

Synthesis of new thiol-derivatized aminophosphines and their catalytic activities in C--C coupling reactions

Keywords:

Aminophosphine, synthesis, catalysis, palladium, Suzuki--Heck,

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of NHPPh2) , 134.78 (C4-Ar), 134.73 (C2-Ar), 132.77 (d, J = 21.1 Hz, o -carbons of NHPPh2) , 129.16 (s, p - carbons of NHPPh2) , 128.50 (d, J = 6.0 Hz, m -carbons of NHPPh2) , 115.68 (C3-Ar); assignment was based on the1H–13C HETCOR and1H–1H COSY spectra;31P{1H} NMR (CDCl3, ppm): δ 36.71 (s). IR (KBr pellet in cm −1 ).epsυ 3278 (N–H) 3147, 3016 (aromatic C–H), 2532 (S–H), 1431 (P–Ph), 738 (P–NH); C18H16NSP
Pongr´acz, P.; Kostas, I. D.; Koll´ar, L. J. Organomet. Chem. 2013, 723, 149–153.
Priyaa, S.; Balakrishna, M. S.; Mobin, S. M.; McDonald, R. J. Organomet. Chem. 2003, 688, 227–235.
Dolinsky, M. C. B.; Lin, W. O.; Dias, M. L. J. Mol. Catal. A: Chem. 2006, 258, 267–274.
Ly, T. Q.; Woollins, J. D. Coord. Chem. Rev. 1998, 176, 451–481.
Fei, Z.; Dyson, P. J. Coord. Chem. Rev. 2005, 249, 2056–2074.
Ghisolfi, A.; Fliedel, C.; Rosa, V.; Monakhov, K. Y.; Braunstein, P. Organometallics 2014, 33, 2523–2534.
Nakajima, T.; Fukushima, Y.; Tsuji, M.; Hamada, N.; Kure, B.; Tanase, T. Organometallics 2013, 32, 7470–7477.
Cimarelli, C.; Fratoni, D.; Palmieri, G. Tetrahedron: Asymmetry 2009, 20, 2234–2239.
Saikia, B.; Boruah, P. R.; Ali, A. A.; Sarma, D. Tetrahedron Lett. 2015, 6, 633–635
Naik, S.; Kumaravel, M.; Mague, J. T.; Balakrishna, M. S. Dalton Trans. 2014, 43, 1082–1095.
Gaw, K. G.; Smith, M. B.; Wright, J. B.; Slawin, A. M. Z.; Coles, S. J.; Hursthouse, M. B.; Tizzard, G. J. J. Organomet. Chem. 2012, 699, 39–47.
Lamblin, M.; Nassar-Hardy, L.; Hierso, J. C.; Fouquet, E.; Felpin, F. X. Adv. Synth. Catal. 2010, 352, 33–79.
Bolliger, J. L.; Frech, C. M. Adv. Synth. Catal. 2010, 352, 1075–1080.
Bolliger, J. L.; Frech, C. M. Chima 2009, 63, 23–28.
Miyaruna, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457–2483.
Whitcombe, N. J.; Hii, K. K.; Gibson, S. E. Tetrahedron 2001, 57, 7449–7476.
Seechurn, C. C. C. J.; Kitching, M. O.; Colacot, T. J.; Snieckus, V. Angew. Chem. Int. Ed. 2012, 51, 5062–5085. 9. Fei, Z.; Scopelliti, R.; Dyson, P. J. Dalton Trans. 2003, 2772–2279.
Fei, Z.; P˘aunescu, E.; Ang, W. H.; Scopelliti, R.; Dyson, P. J. Eur. J. Inorg. Chem. 2014, 1745–1750.
Biricik, N.; Durap, F.; Kayan, C.; G¨umg¨um, B. Heteroatom Chem. 2007, 18, 613–616.
Biricik, N.; Durap, F.; Gumgum, B; Fei, Z.; Scopelliti, R. Trans. Met. Chem. 2007, 32, 877–883.
Zhao, D.; Fei, Z.; Ang, W. H. Cent. Eur. J. Chem. 2008, 6, 93–98.
Biricik, N.; Kayan, C.; G¨umg¨um, B.; Fei, Z.; Scopelliti, R.; Dyson, P. J.; Gurbuz, N.; Ozdemir, I. Inorg. Chim. Acta 2010, 363, 1039–1047.
Kayan, C.; Biricik, N.; Aydemir, M.; Scopelliti, R. Inorg. Chim. Acta 2012, 385, 164–169.
Gaw, K. G.; Smith, M. B.; Slawin, A. M. Z. New J. Chem. 2000, 24, 429–435.
Fei, Z.; Scopellit, R.; Dyson, P. J. Inorg. Chem. 2003, 42, 2125–2130.
Fei, Z.; Biricik, N.; Scopelliti, R.; Dongbin, Z.; Dyson, P. J. Inorg. Chem. 2004, 43, 2228–2230.
Priya, S.; Balakrishna, M. S.; Mague, J. T. J. Organomet. Chem. 2003, 679, 116–124.
Gopalakrishnan, J. Appl. Organomet. Chem. 2009, 23, 291–318.
Ansell, J.; Wills, M. Chem. Soc. Rev. 2002, 31, 259–268.
Appleby, T.; Woollins, J. D. Coord. Chem. Rev. 2002, 235, 121–140.
Bichler, B.; Veiros, L. F.; ¨Oztopcu, O.; Puchberger, M.; Mereiter, K.; Matsubara, K.; Kirchner, K. A. Organometallics , 30, 5928–5942.
Rodriguez, M.; Zubiri, I.; Woollins, J. D. Comment. Inorg. Chem. 2003, 24, 189–252.
Ly, T. Q.; Woollins, J. D. Coord. Chem. Rev . 1998, 176, 451–481.
Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457–2483.
Johnson, B. F. G. Top. Catal. 2003, 24, 147–159.
Suzuki, A. J. Organomet. Chem. 1999, 57, 147–168.
Kotha, S.; Lahiri, K.; Kashninath, D. Tetrahedron Lett. 2002, 9633–9695.
Migowski, P.; Dupont, J. Chem. Eur. J. 2006, 13, 32–39.
Fei, Z.; Geldbach, T. J.; Zhao, D.; Dyson, P. J. Chem. Eur. J. 2006, 12, 2122–2130.
G¨umg¨um, B.; Biricik, N.; Durap , F.; ¨Ozdemir, I.; G¨urb¨uz, N.; Ang, W. H.; Dyson, P. J. Appl. Organometal. Chem. , 21, 711–715. Biricik, N.; Durap, F.; Kayan, C.; G¨umg¨um, B.; G¨urb¨uz, N.; ¨Ozdemir, I.; Ang, W. H.; Fei, Z.; Scopelliti, R. J. Organomet. Chem. 2008, 693, 2693–2699.