Hydrolysis of Phosphonothioates with a Binaphthyl Group: P-Stereogenic O-Binaphthyl Phosphonothioic Acids and Their Use as Optically Active Ligands and Chiral Discriminating Agents

Abstract

The hydrolysis of phosphonothioates with a binaphthyl group afforded the first example of O-(2'-hydroxy)binaphthyl phosphonothioic acids in good to high yields and >95:5 diastereoselectivity. The reaction proceeds via an axis-to-center chirality-transfer reaction. The ability of these acids to act as chiral molecular auxiliaries was demonstrated by using them as optically active ligands for the asymmetric ethylation of benzaldehyde and as a chiral discriminating agent for chiral aliphatic amines.

Hormetic Effects of Binaphthyl Phosphonothioates as Pro-oxidants and Antioxidants

“…The binaphthyl organophosphorus derivatives were synthesized as reported previously and named KK compounds. , DFP was obtained from FUJIFILM Wako Pure Chemicals (Osaka, Japan; cat no. 049-18921).…”

“…Organophosphorous compounds such as binaphthyl phosphono-, phosphorothioates, and their derivatives are useful chiral ligands and metal catalysts for various asymmetric reactions − and are expected to act as heavy metal scavengers . We have previously described a new series of binaphthyl phosphonothioates. , However, the toxicity and biological properties of these new binaphthyl phosphonothioates still needs to be elucidated. Here, we have aimed to evaluate the neurotoxicity and effects of the binapthyhl phosphonothioate compounds shown in Figure on oxidative stress and ER stress, using mouse hippocampal derived neuronal HT22 cells which provide a well-established cellular model for studying endogenous oxidative stress.…”

Synthesis of P‐stereogenic phosphonothioates via alcoholysis of phosphonothioates with a binaphthyl group

“…n ‐BuLi 1.6 mol L −1 solution in hexane was purchased from Mitsuwa Chemical Co., Ltd (Osaka, Japan). Phosphonothioates 1a‐1f were previously prepared . Flash column chromatography was run on silica gel 60 N (spherical neutral) 40‐50 μm of Kanto Chemical Co., Ltd. All manipulations were carried out under argon atmosphere.…”

“…Phosphonothioates 1a-1f were previously prepared. [10] Flash column chromatography was run on silica gel 60 N (spherical neutral) 40-50 μm of Kanto Chemical Co., Ltd. All manipulations were carried out under argon atmosphere. The 1 H NMR spectra were recorded on JEOL ECX-400P (400 MHz) in CDCl 3 .…”

“…In this regard, we have developed a synthesis of phosphorus compounds having both central chirality of a phosphorus atom and axial chirality of a binaphthyl group (Scheme ) during our studies on organochalcogen compounds . We obtained P ‐stereogenic phosphinates II and phosphonothioic acids IV with a binaphthyl group with high diastereoselectivities by reacting phosphonates I and phosphonothioates III with Grignard reagents and metal hydroxides while transferring the axial chirality of the binaphthyl group to the central chirality of the phosphorus atom. We also demonstrated that the obtained phosphonothioic acids can be used as chiral ligands for titanium complexes and show high enantioselectivities in the asymmetric ethylation of benzaldehyde .…”