Investigation of the Asymmetric Addition Reactions Induced by Pentacoordinated Hydrospirophosphorane Substrate

Abstract

Pentacoordinated bisaminoacyl hydrospirophosphoranes were first found to induce the asymmetric addition reactions as a novel chiral organic framework. Asymmetric addition reactions of bisaminoacyl hydrospirophosphoranes with aromatic aldehyde and in situ generated imine were investigated, and the corresponding α-hydroxyspirophosphonates and α-amino spirophosphonates were obtained. The addition reaction of hydrospirophosphoranes with ΔP configuration showed better stereoselectivity than that with ΛP configuration, not only for the addition reaction to aromatic aldehyde but also to in situ generated imine. Furthermore, the stereochemical mechanisms of asymmetric addition reactions induced by pentacoordinated hydrospirophosphorane were proposed by 31P NMR tracing experiment and X-ray diffraction analysis.

NaOAc-Assisted Aerobic Oxidation Protocol for the Synthesis of Pentacoordinate Chalcogenyl Spirophosphoranes with P–Se/P–S Bonds under Open Air

“…A pentacoordinate bis­(aminoacyl)­hydrospirophosphorane synthesized from an amino acid (hereafter AA-HSP) is an ideal model for the study of pentacoordinate phosphorus compounds because of its stable structure, which contains two oxygen ligands, two nitrogen ligands, and two intra-annular carbonyls . Our group has synthesized different optically pure AA-HSPs from amino acids and studied their reaction properties for nearly 20 years, and stereochemical mechanisms that include nucleophilic addition and nucleophilic substitution of AA-HSPs have been proposed …”

“…Our group has been working on the synthesis and chemical properties of pentacoordinate AA-HSPs for nearly 20 years, , and we devote ourselves to exploring the diversity of the reaction of pentacoordinate AA-HSPs as precursors. Over the past several decades, the synthetic methods for constructing P–Se/P–S skeletons using tetracoordinate phosphorus compounds have attracted a great deal of attention from synthetic chemists.…”