77929-23-8Relevant articles and documents
Iridium-catalyzed enantioselective C-H borylation of diarylphosphinates
Song, Shu-Yong,Li, Yinwu,Ke, Zhuofeng,Xu, Senmiao
, p. 13445 - 13451 (2021/11/16)
P-stereogenic phosphorus compounds are a ubiquitous and critically important class of chiral ligands in asymmetric catalysis. Methods for catalytic asymmetric synthesis via a step- and atom-economic way are still very limited. We herein disclose a protocol of phosphinate-directed iridium-catalyzed enantioselective ortho-H borylation to construct P-stereogenic phosphorus compounds. A number of functional groups could be well tolerated to afford optically active diarylphosphinates with good to excellent enantioselectivities (up to 92% ee). We also demonstrate the synthetic utilities of the obtained borylated products, including the synthesis of precursors for chiral phosphine ligands.
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.
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.
