130856-88-1Relevant academic research and scientific papers
Enantiodivergent Formation of C-P Bonds: Synthesis of P-Chiral Phosphines and Methylphosphonate Oligonucleotides
Baran, Phil S.,Eastgate, Martin D.,Knouse, Kyle W.,Padial, Natalia M.,Rivas-Bascón, Nazaret,Schmidt, Michael A.,Vantourout, Julien C.,Xu, Dongmin,Zheng, Bin
, (2020/03/30)
Phosphorus Incorporation (PI, abbreviated Π) reagents for the modular, scalable, and stereospecific synthesis of chiral phosphines and methylphosphonate nucleotides are reported. Synthesized from trans-limonene oxide, this reagent class displays an unexpected reactivity profile and enables access to chemical space distinct from that of the Phosphorus-Sulfur Incorporation reagents previously disclosed. Here, the adaptable phosphorus(V) scaffold enables sequential addition of carbon nucleophiles to produce a variety of enantiopure C-P building blocks. Addition of three carbon nucleophiles to Π, followed by stereospecific reduction, affords useful P-chiral phosphines; introduction instead of a single methyl group reveals the first stereospecific synthesis of methylphosphonate oligonucleotide precursors. While both Π enantiomers are available, only one isomer is required - the order of nucleophile addition controls the absolute stereochemistry of the final product through a unique enantiodivergent design.
Stereoselective catalytic synthesis of P-stereogenic oxides via hydrogenative kinetic resolution
Fernández-Pérez, Héctor,Vidal-Ferran, Anton
supporting information, p. 7019 - 7023 (2019/09/30)
A highly stereoselective catalytic method for the preparation of structurally diverse P-stereogenic oxides has been developed. The approach relies on the ability of rhodium complexes derived from an enantiopure P-OP ligand to kinetically resolve racemic α,β-unsaturated phosphane oxides by hydrogenation of the C= C motif and formation of highly enantioenriched (or even enantiopure) P-stereogenic oxides. The practicality of the methodology has been demonstrated by the preparation of potentially functional P-chiral molecules for catalytic enantioselective synthesis.
Experimental and theoretical investigations of the stereoselective synthesis of P-stereogenic phosphine oxides
Copey, Laurent,Jean-Gérard, Ludivine,Framery, Eric,Pilet, Guillaume,Robert, Vincent,Andrioletti, Bruno
, p. 9057 - 9061 (2015/06/16)
An efficient enantioselective strategy for the synthesis of variously substituted phosphine oxides has been developed, incorporating the use of (1S,2S)-2-aminocyclohexanol as the chiral auxiliary. The method relies on three key steps: 1) Highly diastereoselective formation of PV oxazaphospholidine, rationalized by a theoretical study; 2) highly diastereoselective ring-opening of the oxazaphospholidine oxide with organometallic reagents that takes place with inversion of configuration at the P atom; 3) enantioselective synthesis of phosphine oxides by cleavage of the remaining P-O bond. Interestingly, the use of a PIII phosphine precursor afforded a P-epimer oxazaphospholidine. Hence, the two enantiomeric phosphine oxides can be synthesized starting from either a PV or a PIII phosphine precursor, which constitutes a clear advantage for the stereoselective synthesis of sterically hindered phosphine oxides. That's handy: An efficient enantioselective strategy for the synthesis of variously substituted phosphine oxides was developed, incorporating the use of (1S,2S)-2-aminocyclohexanol as a chiral auxiliary, whereby enantiomeric phosphine oxides can be synthesized starting from either a PV or a PIII phosphine precursor.
THE NUCLEOPHILIC DISPLACEMENT ROUTE TO HOMOCHIRAL ARYLPHOSPHINE OXIDES
Brown, John M.,Carey, Joseph V.,Russell, Michael J.H.
, p. 4877 - 4886 (2007/10/02)
The stereoisomerically pure oxazaphospholidine formed by reaction of (1R,2S)-ephedrine with PhPCl2 is oxidised by ButOOH to the corresponding P-oxide, shown to have R-stereochemistry at phosphorus by X-ray analysis.The product reacts regio- and stereospecifically with o-anisylmagnesium bromide to give the product formed by P-O fission with retention of configuration, which was also characterised by X-ray diffraction.The ephedrine residue was replaced by O-methyl under acid catalysis with inversion of configuration.Attempts to incorporate p-fluorophenyl using similar conditions led to isolation of the pyrophosphinate in low yield.The OMe residue in the methoxyphosphinate was readily displaced by aliphatic or aromatic Grignard reagents giving the corresponding phosphine oxides with inversion of configuration.This procedure constitutes a simple route to di- and triarylphosphine oxides in ca. 95percent e.e.; optical purities were estimated by NMR methods.
