Catalytically atroposelective ring-opening of configurationally labile compounds to access axially chiral biaryls

Abstract

Axially chiral biaryls scaffolds are vital in natural products, pharmaceuticals, and asymmetric synthesis. Catalytically atroposelective ring-opening of configurationally labile compounds, pioneered by Bringmann, has received continuous attention in the past...

Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage

“…This In the past 20 years, the opening of five-membered rings has emerged as a strategy for dynamic kinetic resolutions due to the rapid rates of racemization typically observed for biaryls constrained in a bridging five-membered ring. 250 These strategies have been enabled by advancements in metal-mediated activation of alternative cross-coupling electrophiles and has been applied to the dynamic kinetic ring opening of diarylfurans, diaryl iodoniums, dithiofurans, and silafluorenes, which will be discussed in detail below.…”

Developing Biarylhemiboronic Esters for Biaryl Atropisomer Synthesis via Dynamic Kinetic Atroposelective Suzuki–Miyaura Cross-Coupling

“…Therefore, considerable efforts have been dedicated to their catalytic asymmetric synthesis over the years . In this context, dynamic kinetic asymmetric ring-opening transformation of configurationally labile bridged biaryls has been emerging as a highly useful approach to access biaryl atropisomers . The state-of-the-art tactic employs the five- and six-membered bridging rings .…”

Advances in Atroposelectively De Novo Synthesis of Axially Chiral Heterobiaryl Scaffolds

“…These diverse methodologies can be divided into four main categories ( Figure 2 ): (A) atroposelective coupling of two aromatic sub-units [ 33 , 34 , 35 , 36 ], (B) transformation of prochiral heterobiaryl molecules into axially chiral skeletons [ 37 , 38 , 39 , 40 ], (C) central-to-axial chirality conversion [ 41 , 42 , 43 ], and (D) de novo construction of axially chiral molecules [ 44 , 45 , 46 ]. To date, several elegant reviews have been disclosed, in which the authors focused on the atroposelective coupling of two units [ 47 , 48 ], atroposelective transformation of prochiral heterobiaryls [ 11 , 49 , 50 , 51 ], and central-to-axial chirality conversion [ 52 , 53 ]. Although de novo synthesis of axially chiral heterobiaryl exhibits highly convergent and superior atom economy, atroposelective construction of the heterobiaryl subunits by de novo synthesis was rarely covered.…”