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

Abstract

The reaction of phosphonothioates having a binaphthyl group with alkoxides proceeded via transfer of the axial chirality of the binaphthyl group to the central chirality of the phosphorus atom to give P‐stereogenic phosphonothioates with moderate‐to‐excellent diastereoselectivities. The reaction of phosphonoselenoates also proceeded in a similar fashion. The selenium atom of the obtained product could be excluded with tributylphosphine to give a trivalent phosphonite, which was isolated as a boron complex.

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).…”

“…The binaphthyl organophosphorus derivatives were synthesized as reported previously and named KK compounds. 20 Cell Culture. The HT22 immortalized hippocampal cell line was a kind gift from David Schubert, The Salk Institute, La Jolla, CA, USA.…”

“…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.…”

Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes

“…The stereochemistry on a phosphorus atom has not received much attention, despite the fact that the introduction of at least three different substituents to the phosphorus atom gives rise to the stereogenic center on the phosphorus atom. During the course of our studies on main group chemistry [39,40], we have intensively studied the synthesis and applications studies on main group chemistry [39,40], we have intensively studied the synthesis and applications of organophosphorus compounds with a binaphthyl group [41][42][43][44][45] and recently reported that the deprotonation and alkylation of phosphonoselenoates and phosphonates with a binaphthyl group creates stereogenic secondary and tertiary carbon centers adjacent to the phosphorus atom with high diastereoselectivity (Scheme 1a,b) [46]. The resulting products are potentially available as precursors of primary phosphines since phosphorus-oxygen bonds are readily reduced to P-H bonds.…”

Chemoselective and Stereoselective Alcoholysis of Binaphthyl Phosphonothioates: Straightforward Access to Both Stereoisomers of Biologically Relevant P-Stereogenic Phosphonothioates

“…However, the preparation of these P -stereogenic templates generally requires the separation of their diastereomers by recrystallization or silica gel column chromatography . In this regard, we have demonstrated that an axis-to-center chirality transfer of phosphonates and phosphonothioates having a binaphthyl group with carbon nucleophiles and metal hydroxides leads to the formation of P -stereogenic organophosphorus compounds . For example, the reaction of phosphonothioates 2 , which are easily prepared from phosphorus trichloride, elemental sulfur, Grignard reagents, and optically active 1,1′-bi-2-naphthol (BINOL), with alkoxides gives P -stereogenic compounds via an axis-to-center chirality transfer (Scheme B) .…”