Related Experiment Video
Updated: May 23, 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
Phosphino hydrazones as suitable ligands in the asymmetric Suzuki-Miyaura cross-coupling
Abel Ros1, Beatriz Estepa, Antonio Bermejo
1Instituto de Investigaciones Químicas (IIQ), CSIC/US, Américo Vespucio 49, 41092 Seville, Spain.
Abstract:
Phosphino hydrazones derived from C(2)-symmetric hydrazines exhibit excellent catalytic activity and provide good enantioselectivities in the asymmetric Suzuki-Miyaura cross-coupling to axially chiral biaryls, in particular for the most challenging reactions of monocyclic, functionalized aryl bromides and triflates. X-ray analysis of preformed [Pd(P/N)Cl(2)] precatalysts [(P/N) = phosphino hydrazone] revealed a strong n-π conjugation in the hydrazone moiety, identified by a high planarity degree at the pyrrolidine N(sp(3)) atom, that makes rotations around N-N bonds inconsequential. The complexes are also characterized by an envelope-like conformation with the Pd atom placed at the opposite side to the 2-phenyl group on the nearest stereogenic center of the pyrrolidine group. The isolation and structural analysis of oxidative addition intermediates indicate that the configurational stability of Pd-C(Ar) bonds is dependent on the substitution pattern in the aryl bromide.
Related Concept Videos
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo, or cyano...
Preparation and Reactions of Sulfides
Aryldiazonium Salts to Azo Dyes: Diazo Coupling
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Aldehydes and Ketones to Alkenes: Wittig Reaction Overview
