Asymmetric Synthesis of Chiral Atropisomeric Bis-Aryl Organophosphorus from Menthyl H-Phosphinate

Abstract

This review describes new methods for the synthesis of chiral monophosphine ligands with menthyl phenylphosphinate as a chiral auxiliary through asymmetric Suzuki-Miyaura cross-coupling reactions and asymmetric C-H functionalization. The chiral menthyl phenylphosphinate as a chiral auxiliary is easy to prepare and the menthyl group can easily be transformed into other functional groups, with the chiral center synchronously remaining. These methodologies provide highly efficient and practical strategies for the synthesis of novel axially chiral biaryl monophosphine oxides and their corresponding phosphines. Meanwhile, these reactions are easy to handle and exhibit wide scope for substrates with excellent diastereomeric ratios.

Nucleophilic Substitution of P-Stereogenic Chlorophosphines: Mechanism, Stereochemistry, and Stereoselective Conversions of Diastereomeric Secondary Phosphine Oxides to Tertiary Phosphines

“…The stereogenic secondary phosphine oxides (SPO) can be easily converted to tertiary phosphines oxides (TPO) via alkylating, cross-coupling, addition (Figure ), − and halogenation followed by substitution with metallic reagents, with good stereoselectivity. However, the optically pure SPOs are difficult to acquire .…”

The Catalytic Formation of Atropisomers and Stereocenters via Asymmetric Suzuki–Miyaura Couplings

“…A few years later, Yang’s group reported the use of chiral phosphinate auxiliary to achieve the formation of axially chiral biaryls with excellent diastereoselectivities and good yields. , Likewise, the scope is also limited to bromoarylphosphinate electrophile with the demonstration on only two examples (Scheme B). Recently, Cheon and co-workers reported the use of a chiral amine directing group to achieve the formation of several alkaloids, including Ancistrotanzanine B, Ancistrotectoriline A, and various of their derivatives .…”

Functional Phosphine Derivatives Having Stationary and Flexible Chiralities: Their Preparation and Chirality Controlling

“…Chiral tertiary phosphines (CTPs) are widely applied in asymmetric catalysis as ligands of metallic catalysts and as organocatalysts, which contain either chiral carbon skeleton or stereogenic phosphorus atom. − The CTPs, even for that have sole chirality, are usually acquired from multistep conversions or via tedious kinetic resolutions . A chiral auxiliary is usually employed for the preparation of P- stereogenic CTPs, via alkylating, cross-coupling, addition, and substitution. − The lengthy synthesis route probably results in chirality loss so that the reactions are usually performed under harsh conditions such as low temperature or strong alkali reagents…”