77929-22-7Relevant 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
supporting information, (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.
Chemo-, regio- and stereoselective conversion of P-chirogenic phosphorus borane complexes into their P=O or P=S derivatives
Uziel, Jacques,Darcel, Christophe,Moulin, Dominique,Bauduin, Christophe,Juge, Sylvain
, p. 1441 - 1449 (2007/10/03)
Chiral and achiral organophosphorus borane complexes are readily transformed into their corresponding phosphoryl or thiophosphoryl compounds in high yields using one-pot procedures with stereoselectivities reaching 100% in many cases. Both oxidation and sulfuration were performed under neutral or mild conditions and were applied to various organophosphorus borane complexes (phosphines, phosphinates, chlorophosphines, aminophosphines, etc.). In the case of the dissymmetric diphosphine or aminophosphine phosphinite ligands, the reaction of their diborane complexes proceeds regiospecifically to a single phosphorus group, affording the corresponding hybrid derivatives.
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.
GRIGNARD REACTION OF 2-PHENYL-TETRAHYDROPYRROLO-1,3,2-OXAZAPHOSPHOLES, OBSERVATION OF THE STEREOSPECIFIC INVERSION OF CONFIGURATION
Koizumi, Toru,Yanada, Reiko (nee Ishizaka),Takagi, Hiroyasu,Hirai, Hajime,Yoshii, Eiichi
, p. 571 - 572 (2007/10/02)
Grignard reaction of bicyclic oxazaphospholes proceeded with inversion of configuration to provide chiral phosphinic esters of known absolute configurations.
