In the transition-metal-catalyzed cross-coupling reactions, the use of the first row transition metals as catalysts is much more appealing than the precious metals owing to the apparent advantages such as cheapness and earth abundance. Within the last two decades, particularly the last five years, explosive interests have been focused on the nickel-catalyzed Suzuki–Miyaura reactions. This has greatly advanced the chemistry of transition-metal-catalyzed cross-coupling reactions. Most notably, a broad range of aryl electrophiles such as phenols, aryl ethers, esters, carbonates, carbamates, sulfamates, phosphates, phosphoramides, phosphonium salts, and fluorides, as well as various alkyl electrophiles, which are conventionally challenging, by applying palladium catalysts can now be coupled efficiently with boron reagents in the presence of nickel catalysts. In this review, we would like to summarize the progress in this reaction.

Transition-metal-catalyzed Suzuki-Miyaura cross-coupling reactions: a remarkable advance from palladium to nickel catalysts

The stereocontrolled construction of C−C bonds remains one of the foremost challenges in organic synthesis. At the heart of any chemical synthesis of a natural product or designed small molecule is the need to orchestrate a series of chemical reactions to prepare and functionalize a carbon framework. The advent of transition-metal catalysis has provided chemists with a broad range of new tools to forge C−C bonds and has resulted in a paradigm shift in synthetic strategy planning. The impact of these methods was recognized with the awarding of the 2010 Nobel Prize in Chemistry to Richard Heck, Ei-ichi Negishi, and Akira Suzuki for their seminal contributions to the development of Pd-catalyzed cross-coupling.

Enantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C–C Bonds

Axial chirality is a key feature of many important organic molecules, such as biologically active compounds, stereogenic ligands and optically pure materials. Significant efforts in the field of the atropisomeric synthesis of biaryls have hence been undertaken over the past decade. Several major improvements of the already known methods to build up such chiral backbones (e.g. oxidative couplings and stereoselective Suzuki–Miyaura arylations) have been achieved and, in parallel, novel concepts have emerged enabling unprecedented synthetic routes toward molecules of this kind. These outstanding steps further unlocked the door to the preparation of previously difficult-to-access precursors of privileged ligands like BINOL, BINAM, QUINAP and many other molecules of interest.

Recent advances and new concepts for the synthesis of axially stereoenriched biaryls

Metal-catalyzed asymmetric processes offer one of the most straightforward ways to introduce stereogenic centers Hence, the development of novel chiral ligands that can effectively induce asymmetry in reactions is crucial in modern organic synthesis While many established chiral ligands bind to a metal through heteroatoms, structures that coordinate to metals through carbon atoms have received little attention so far Here, we highlight the increasing number of such chiral chelating olefin ligands as well as their application in a variety of metal-catalyzed transformations

Chiral olefins as steering ligands in asymmetric catalysis.

Rhodium-catalyzed asymmetric arylation (RCAA) reactions provide one of the most straightforward and powerful ways to introduce aryl fragments in an enantioselective manner. The discovery of novel chiral ligands and catalytic systems is a major focus in generating optical chiralities for RCAA reactions. In the past decade, the chelating functionalities in ligands have been significantly expanded from traditional phosphorus to interesting diene, bissulfoxide, and their hybrids. Herein we highlight the research on these distinct families of chiral ligands and describe their applications in the RCAA of arylmetals to activated alkenes, aldehydes, ketones and imines, and RCAA-tandem reactions.

Rhodium-Catalyzed Asymmetric Arylation

A new type of C2-symmetric chiral diene ligand bearing a simple bicyclic [3.3.0] backbone was discovered. (3aS,6aS)-3,6-diphenyl-1,3a,4,6a-tetrahydropentalene was applied successfully in the Rh-catalyzed asymmetric arylation of N-tosylarylimines with arylboronic acids. With the new chiral diene ligand, a broad range of highly enantiomerically enriched diarylmethylamines (98−99% ee) as well as 3-aryl substituted phthalimidines (99% ee) could be easily prepared.

Design of C2-symmetric tetrahydropentalenes as new chiral diene ligands for highly enantioselective Rh-catalyzed arylation of N-tosylarylimines with arylboronic acids.

The title reaction proceeds with high enantioselectivity to give a broad range of synthetically useful β,β-disubstituted nitroalkanes.

Rhodium-catalyzed asymmetric conjugate addition of organoboronic acids to nitroalkenes using chiral bicyclo[3.3.0] diene ligands.

Chiral Diene as the Ligand for the Synthesis of Axially Chiral Compounds via Palladium-Catalyzed Suzuki−Miyaura Coupling Reaction

Highly practical catalytic asymmetric 1,4-addition of arylboronic acids in water using new hydrophilic chiral bicyclo[3.3.0] diene ligands

The synthesis of a new type of C(2)-symmetric chiral diene ligands with a nonbridged bicyclic [3.3.0] backbone was successfully introduced. Using highly efficient lipase-catalyzed transesterification and Suzuki-coupling strategies, a broad family of enantiopure 3,6-disubstituted bicyclo[3.3.0] dienes with different electronic and steric properties could be easily prepared. The application of these new diene ligands in the Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds have been examined, and excellent enantioselectivities (up to 98 % ee) as well as good yields are achieved under very mild reaction conditions at room temperature.

Zhi-Qian Wang

Papers

Design of C2-symmetric tetrahydropentalenes as new chiral diene ligands for highly enantioselective Rh-catalyzed arylation of N-tosylarylimines with arylboronic acids.

Rhodium-catalyzed asymmetric conjugate addition of organoboronic acids to nitroalkenes using chiral bicyclo[3.3.0] diene ligands.

Chiral Diene as the Ligand for the Synthesis of Axially Chiral Compounds via Palladium-Catalyzed Suzuki−Miyaura Coupling Reaction

Highly practical catalytic asymmetric 1,4-addition of arylboronic acids in water using new hydrophilic chiral bicyclo[3.3.0] diene ligands

Easily Accessible C2-Symmetric Chiral Bicyclo[3.3.0] Dienes as Ligands for Rhodium-Catalyzed Asymmetric 1,4-Addition