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Updated: May 30, 2026
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Air-stable Pd(R-allyl)LCl (L= Q-Phos, P(t-Bu)3, etc.) systems for C-C/N couplings: insight into the
Carin C C Johansson Seechurn1, Sébastien L Parisel, Thomas J Colacot
1Johnson Matthey Catalysis & Chiral Technologies, Orchard Road, Royston, SG8 5HE, UK.
Abstract:
A series of Pd(R-allyl)LCl complexes [R = H, 1-Me, 1-Ph, 1-gem-Me(2), 2-Me; L = Q-Phos, P(t-Bu)(3), P(t-Bu)(2)(p-NMe(2)C(6)H(4)), P(t-Bu)(2)Np] have been synthesized and evaluated in the Buchwald-Hartwig aminations in detail, in addition to the preliminary studies on Suzuki coupling and α-arylation reactions. Pd(crotyl)Q-PhosCl (9) was found to be a superior catalyst to the other Q-Phos-based catalysts, and the reported in situ systems, in model coupling reactions involving 4-bromoanisole substrate with either N-methylaniline or 4-tert-butylbenzeneboronic acid. Precatalyst 9 also performed better than the catalysts bearing P(t-Bu)(2)(p-NMe(2)C(6)H(4)) ligand; however, it is comparable to the new crotyl catalysts bearing P(t-Bu)(3) or P(t-Bu)(2)Np ligands. In α-arylation of a biologically important model substrate, 1-tetralone, Pd(allyl)P(t-Bu)(2)(p-NMe(2)C(6)H(4))Cl (15) was found to be the best catalyst. The reason for the relatively higher activity of the crotyl complexes in comparison to the allyl derivatives in C-N bond formation reactions was investigated using X-ray crystallography in conjunction with NMR spectroscopic studies.
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