Murat AYDEMİR, Feyyaz DURAP, Akin BAYSAL

New Pd(II) and Pt(II)-diaminophosphine complexes bearing cyclohexyl or isopropyl moiety: use of Pd(II) complexes as precatalyst in Mizoroki--Heck and Suzuki--Miyaura cross-coupling reactions

Two new diaminophosphine ligands, $N$,$N$'-bis(dicyclohexylphosphino)-2-(aminomethyl)aniline (\textbf{1}) and $N$,$N$'-bis(diisopropylphosphino)-2-(aminomethyl)aniline (\textbf{2}) were synthesized by the reaction of 2-(aminomethyl)aniline with two equivalents of Cy$_{2}$PCl or (iPr)$_{2}$PCl, respectively. The reactions of \textbf{1 }and \textbf{2} with MCl$_{2}$(cod) (M = Pd, Pt; cod = 1,5-cyclooctadiene) yield complexes [\textit{cis}-Pd(L$_{2}$\textbf{P}NHC$_{6}$H$_{4}$CH$_{2}$NH\textbf{P}L$_{2})$Cl$_{2}$] (L = Cy \textbf{3}, iPr \textbf{4}) and [\textit{cis}-Pt(L$_{2}$\textbf{P}NHC$_{6}$H$_{4}$CH$_{2}$NH\textbf{P}L$_{2})$Cl$_{2}$] (L = Cy \textbf{5}, iPr \textbf{6}), respectively. The catalytic activity of the palladium complexes was investigated in the Suzuki--Miyaura cross-coupling reaction in the presence of Cs$_{2}$CO$_{3}$ as a base. The palladium complexes were also found to be highly active catalysts in the Mizoroki--Heck reaction.

Anahtar Kelimeler:

Diaminophosphine, palladium, platinum, Suzuki reaction, Heck reaction, stilbene

New Pd(II) and Pt(II)-diaminophosphine complexes bearing cyclohexyl or isopropyl moiety: use of Pd(II) complexes as precatalyst in Mizoroki--Heck and Suzuki--Miyaura cross-coupling reactions

Keywords:

Diaminophosphine, palladium, platinum, Suzuki reaction, Heck reaction, stilbene,

PDF

___

McAuliﬄe, C. A. Comprehensive Coordination Chemistry ; Pergamon: Oxford, UK, 1987, 2, pp. 989–1060.
Drent, E.; Van-Brockhoven, J. A. M.; Doyle, M. J. J. Organomet. Chem. 1991, 417, 235–251.
Joshi, M. J.; Thornburn, S. J.; Retting, S. J.; James, B. R.; Inorg. Chim. Acta. 1992, 283, 198–200.
Kang, Y. B.; Pabel, M.; Pathak, D. D.; Willis, A. C.; Wild, S. B. Main Group Chem. 1995, 1, 89–98.
Ugo, R. Aspects of Homogeneous Catalysis, A Series of Advances; Reiedel: Dordrecht, Holland, 1974.
Benito-Garagorni, D.; Bocokic, V.; Mereiter, K.; Kirchner, K. Organometallics 2006, 25, 3817–3823.
Biricik, N.; Durap, F.; Kayan, C.; G¨umg¨um, B. Heteroatom Chem. 2007, 18, 613–616.
Ittel, S.; Parshall, G. Homogeneous Catalysis, the Applications and Chemistry of Catalysis by Soluble Transition
Metal Complexes; Wiley: New York, NY, USA, 1992.
Appleby, T.; Aucott, S. M.; Clarke, M. L.; Slawin, A. M. Z.; Woollins, J. D. Polyhedron 2002, 21, 2639–2645.
Aydemir, M.; Baysal, A.; G¨urb¨uz, N.; ¨Ozdemir, ˙I.; G¨umg¨um, B.; ¨Ozkar, S.; C¸ aylak, N.; Yıldırım, L. T. Appl.
Organomet. Chem. 2010, 24, 17–24. 11.Akba, O.; Durap, F.; Aydemir, M.; Baysal, A.; G¨umg¨um, B.; ¨Ozkar, S. J. Organomet. Chem. 2009, 694, 731–736. 12.G¨umg¨um, B.; Biricik, N.; Durap F.; ¨Ozdemir, ˙I.; G¨urb¨uz, N.; Ang, W. H.; Dyson, P. J. Appl. Organomet. Chem.
, 21, 711–715. 13.Aydemir, M.; Baysal, A.; S¸ahin, E.; G¨umg¨um, B. Inorg. Chim. Acta 2011, 378, 10–18. 14.Kayan, C.; Biricik, N.; Aydemir, M. Trans. Met. Chem. 2012, 36, 513–520. 15.Kılı¸c, A.; Durap, F.; Aydemir, M.; Baysal, A.; Ta¸s, E. J. Organomet. Chem. 2008, 693, 2835. 16.Elma, D.; Durap, F.; Aydemir, M.; Baysal, A.; Meri¸c, N.; Baysal, A.; Meri¸c, N.; Ak, B.; Turgut, Y.; G¨umg¨um, B.
Lloyd-Williams, P.; Giralt, E.; Chem. Soc. Rev. 2001, 30, 145–147.
Bedford, R. B. Chem. Commun. 2003, 1787–1796.
Najera, C.; Gil-Molto, J.; Karlstr¨om, S.; Falvello, L. R. Org. Lett. 2003, 5, 1451–1454.
Galon, B. J.; Kojima, R. W.; Kaner, R. B.; Diaconescu, P. L. Angew. Chem. Int. Ed. 2007, 46, 7251–7254.
Trost, B. M.; Flemming, I.; Semmelhack M. F. Comprehensive Organic Synthesis, vol. 4 ; Pergamon Press: Oxford, UK, 1991.
Cabri, W.; Candiani, I. Acc. Chem. Res. 1995, 28, 2–7.
Brunner, H.; Le Cousturier de Courey, N.; Genet, J. P. Tetrahedron Lett. 1999, 40, 4815–4818. 40.Herrmann, W. A.; Broßmer, C.; ¨Ofele, K.; Reisinger, C.; Riermeier, T.; Beller, M.; Fischer, H. Angew. Chem. 1995, 107, 1989–1992.
Drew, D.; Doyle, J. R. Inorg. Synth. 1972, 13, 47–55. 42.McDermott, J. X.; White, J. F.; Whitesides, G. M. J. Am. Chem. Soc. 1976, 98, 6521–6528.