35143-99-8Relevant academic research and scientific papers
Reduction of tertiary phosphine oxides to phosphine-boranes using Ti(Oi-Pr)4/BH3-THF
Sowa, Sylwia,Pietrusiewicz, K. Micha?
, (2021/03/17)
A new method for reduction of tertiary phosphine oxides leading to the formation of tertiary phosphine-boranes has been developed. The BH3-THF/Ti(Oi-Pr)4 reducing system enables conversion of triaryl, diarylalkyl and trialkylphosphine oxides directly to their borane analogues in good to high yields. In contrast to the previously reported protocols, the presence of activating groups in the structure of starting material is not necessary for the reaction to occur. The reaction is highly stereoselective and proceeds with predominant retention of configuration at the phosphorus atom. A plausible mechanism of reduction of the P[dbnd]O bond by BH3-THF/Ti(Oi-Pr)4 has been proposed.
A facile and practical preparation ofP-chiral phosphine oxides
Xu, Ronghua,Gao, Zhenhua,Yu, Yiteng,Tang, Yehua,Tian, Duanshuai,Chen, Tian,Chen, Yibing,Xu, Guangqing,Shi, Enxue,Tang, Wenjun
, p. 3335 - 3338 (2021/04/07)
A practical and cost-effective synthetic method ofP-chiral diarylalkyl, aryldialkyl, and triaryl phosphine oxides by using readily available chiral diphenyl-2-pyrrolidinemethanol as the auxiliary is developed. The long-standing racemization issue during s
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 Synthesis of Both PAMPO Enantiomers Using l -Menthyl Chloroacetate and Stereomutation at P in Classical Quaternisation Reactions
Dziuba, Kamil,Lubańska, Ma?gorzata,Pietrusiewicz, K. Micha?
, p. 909 - 916 (2020/03/13)
A practical protocol for efficient synthesis of both PAMPO enantiomers as well as related functionalised P-stereogenic phosphine oxides in 1-3 steps from effectively resolved (S P)- l -menthyl o -anisyl-(phenyl)phosphinylacetate has been develo
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.
P-Chiral Phosphines Enabled by Palladium/Xiao-Phos-Catalyzed Asymmetric P-C Cross-Coupling of Secondary Phosphine Oxides and Aryl Bromides
Dai, Qiang,Li, Wenbo,Li, Zhiming,Zhang, Junliang
supporting information, p. 20556 - 20564 (2019/12/27)
The development of transition-metal-catalyzed methods for the synthesis of P-chiral phosphine derivatives poses a considerable challenge. Herein, we present a direct Pd/Xiao-Phos-catalyzed cross-coupling reaction of easily accessible secondary phosphine o
Desymmetrization of Phosphinic Acids via Pd-Catalyzed Asymmetric Allylic Alkylation: Rapid Access to P-Chiral Phosphinates
Trost, Barry M.,Spohr, Simon M.,Rolka, Alessa B.,Kalnmals, Christopher A.
, p. 14098 - 14103 (2019/10/11)
The synthesis of P-chiral compounds is challenging, especially since useful catalytic methods for preparing such molecules are scarce. Herein we disclose a desymmetrization that employs phosphinic acids as prochiral nucleophiles in a Pd-catalyzed asymmetr
D-Glucosamine as a novel chiral auxiliary for the stereoselective synthesis of P-stereogenic phosphine oxides
D'Onofrio,Copey,Jean-Gérard,Goux-Henry,Pilet,Andrioletti,Framery
, p. 9029 - 9034 (2015/09/01)
D-Glucosamine was successfully employed as a chiral auxiliary for the enantioselective synthesis of phosphine oxides. The influence of the anomeric position was also investigated and revealed the excellent ability of the α-anomer to perform this transform
Hammond Postulate Mirroring Enables Enantiomeric Enrichment of Phosphorus Compounds via Two Thermodynamically Interconnected Sequential Stereoselective Processes
Rajendran, Kamalraj V.,Nikitin, Kirill V.,Gilheany, Declan G.
, p. 9375 - 9381 (2015/08/06)
(Figure Presented). The dynamic resolution of tertiary phosphines and phosphine oxides was monitored by NMR spectroscopy. It was found that the stereoselectivity is set during the formation of the diastereomeric alkoxyphosphonium salts (DAPS), such that t
Method for manufacturing a new dephosphorizing ligand homochiral (by machine translation)
-
Paragraph 0128; 0129; 0130; 0136, (2016/10/10)
Disclosed are methods for making chiral phosphorus ligands including chiral phosphines, chiral phosphine oxides, phosphonamides, and aminophosphines. The chiral phosphorus ligands prepared by the methods of the invention are useful as components of chiral catalysts, e.g., transition metal complexes.
