Catalytic Kinetic Resolution of Biaryl Compounds

Abstract

Biaryl compounds with axial chirality are very common in synthetic chemistry, especially in catalysis. Axially chiral biaryls are important due to their biological activities and extensive applications in asymmetric catalysis. Thus the development of efficient enantioselective methods for their synthesis has attracted considerable attention. This Minireview discusses the progress made in catalytic kinetic resolution of biaryl compounds and chronicles significant advances made recently in catalytic kinetic resolution of biaryl scaffolds.

Atroposelective Synthesis of Axially Chiral Biaryls by Palladium‐Catalyzed Asymmetric C−H Olefination Enabled by a Transient Chiral Auxiliary

“…[1] Accordingly,g reat efforts have been devoted to the efficient synthesis of these chiral frameworks, [2] including asymmetric coupling of two arenes by oxidative dimerization or cross-coupling, [3] atroposelective aryl formation by cycloaddition, [4] asymmetric ringopening of bridged biaryls, [5] asymmetric transfer hydrogenation, [6] stereoselective functionalization of prochiral or racemic biaryls, [7,8] and others. [1] Accordingly,g reat efforts have been devoted to the efficient synthesis of these chiral frameworks, [2] including asymmetric coupling of two arenes by oxidative dimerization or cross-coupling, [3] atroposelective aryl formation by cycloaddition, [4] asymmetric ringopening of bridged biaryls, [5] asymmetric transfer hydrogenation, [6] stereoselective functionalization of prochiral or racemic biaryls, [7,8] and others.…”

Practical and Scalable Kinetic Resolution of BINOLs Mediated by a Chiral Counterion

“…[5,6] This is av aluable technique for obtaining extremely high levels of enantioenrichment in unreacted substrate through high selectivity factors (s)a nd control of conversion. Previous approaches to the KR [7] of BINOLs include Tsujisp alladium catalyzed alcoholysis of vinyl ether derivatives using ac hiral diamine ligand, which enabled the recovery of enantioenriched unreacted substrate with s up to 36 ( Figure 1A). [8] An alternative approach from the Sibi group ( Figure 1B) involves employing ac hiral 4-dimethylaminopyridine equivalent to enable enantioselective O-acylation of am onofunctionalized BINOL derivative with s up to 38.…”

Atropoenantioselective Redox‐Neutral Amination of Biaryl Compounds through Borrowing Hydrogen and Dynamic Kinetic Resolution

“…This protocol features broad substrate scope and good functional-group tolerance, and allows the rapid assembly of axially chiral biaryl compounds in good to high yields and with high to excellent enantioselectivity.Because of their unique molecular architectures and conformational behavior, [1] axially chiral biaryl molecules are of interest for potential applications in organic chemistry,d rug discovery,a nd material sciences. This protocol features broad substrate scope and good functional-group tolerance, and allows the rapid assembly of axially chiral biaryl compounds in good to high yields and with high to excellent enantioselectivity.…”

“…Because of their unique molecular architectures and conformational behavior, [1] axially chiral biaryl molecules are of interest for potential applications in organic chemistry,d rug discovery,a nd material sciences. [2] In asymmetric catalysis, axially chiral biaryl structures,asexamplified by BINOL and BINAP,h ave served as privileged scaffolds for the development of chiral ligands,catalysts,and auxiliaries.…”

“…[2] In asymmetric catalysis, axially chiral biaryl structures,asexamplified by BINOL and BINAP,h ave served as privileged scaffolds for the development of chiral ligands,catalysts,and auxiliaries. [2,3] Stimulated by the continually growing demand for axially chiral biaryl compounds, [1,2] much attention has focused on the exploration of novel asymmetric methods.T wo traditional approaches, that is,the optical resolution of racemic materials and chiralauxiliary-based diastereoselective synthesis,are still restricted to the use of as toichiometric amount of chiral reagents. [4] Catalysis seems to be an ideal solution to this problem.…”