Sequential and iterative Pd-catalyzed cross-coupling reactions in organic synthesis

Abstract

Sequential and iterative Pd-catalyzed cross-coupling reactions can be performed in which the order of C–C bond formations can be controlled either by the attenuated leaving groups of the multireactive substrate or by specific catalyst/ligand combinations. This tutorial review gives an overview about recent developments in this field and the various strategies used for the assembly of oligoarenes and -alkenes.Graphical abstract

Murahashi Cross‐Coupling at −78 °C: A One‐Pot Procedure for Sequential C−C/C−C, C−C/C−N, and C−C/C−S Cross‐Coupling of Bromo‐Chloro‐Arenes

“…This methodology would allow divergent synthesis to be achieved in an efficient manner, providing a powerful tool for synthesis. Methodology for the sequential coupling of two sp 2 hybridized organometallic reagents with a dihalide electrophile is known, but a general cross‐coupling procedure in which one of the coupling partners is a sp 3 hybridized nucleophile is less prevalent . Small alkyl fragments, and in particular secondary (branched) centers, are crucial for the development of potent biomedically active compounds that bind with high selectivity to their protein targets .…”

Phosphonium Salts as Pseudohalides: Regioselective Nickel‐Catalyzed Cross‐Coupling of Complex Pyridines and Diazines

“…As phosphonium ions are uncommon functional groups for cross-coupling reactions,w eq uestioned whether they could be used orthogonally to halides and enable iterative coupling sequences. [18] Negishi and Suzuki reactions are possible where the palladium catalyst reacts exclusively with the CÀBr bond in 1ac,l eaving the phosphonium ion for further transformation (1n and 1ad;S chemes 2a,b). Palladium catalysis must be used to achieve orthogonality as our nickel catalysis protocol results in mixtures of mono-and diarylated products.…”

The Use of Palladium on Magnetic Support as Catalyst for Suzuki–Miyaura Cross-Coupling Reactions

“…Since the discovery of the Suzuki-Miyaura cross-coupling reaction in 1979 (Scheme 1) [1][2][3], it has become one of the most utilized cross-coupling reactions both in industrial and academic research laboratories [3][4][5][6][7]. For the development of this reaction Suzuki was awarded the 2010 Nobel prize in chemistry, together with Negishi and Heck, the chemists behind the Negish coupling and Heck coupling, respectively [8][9][10].…”

“…Homogeneous palladium catalyst systems have, by far, been the most dominating catalysts utilized for this cross-coupling reaction [7]. In addition to the catalyst many reactions also require the Scheme 1.…”

“…Since the early reports by Suzuki and Miyaura on the cross-coupling reaction a tremendous development has taken place in terms of substrate flexibility and reaction conditions. A range of different catalysts and conditions are now available for the successful cross-coupling of halides, triflates, O-tosylates, and diazonium salts upon reaction with boronic acid, boronates, and trifluoroborates [3,7,[11][12][13][14][15]]. …”