1312032-05-5Relevant articles and documents
Construction of P-Chiral Alkenylphosphine Oxides through Highly Chemo-, Regio-, and Enantioselective Hydrophosphinylation of Alkynes
Dai, Qiang,Li, Wenbo,Liu, Lu,Qian, Yanyan,Zhang, Junliang
, p. 20645 - 20650 (2020)
Alkenylphosphine oxides have a wide spectrum of practical applications. However, chemo-, regio-, and enantiocontrolled construction of this structural motif still constitutes a significant synthetic challenge. Here we show that these compounds can be efficiently accessed by using a palladium/Xiao-Phos catalytic system, which leads to the highly regioselective formation of the anti-Markovnikov adducts through addition of a secondary phosphine oxide to an alkyne. Diverse (hetero)aryl and alkyl alkynes, as well as both terminal and internal alkynes can be employed as substrates. The kinetic resolution process makes it possible to produce alkenylphosphine oxide and recovered secondary phosphine oxides with high ee values. Further transformations of these two P-chiral scaffolds confirm the high practicability and application prospect of our synthetic strategies. Initial mechanistic studies strongly suggested that hydropalladation is likely responsible for the conversion process.
Asymmetric Library Synthesis of P-Chiral t-Butyl-Substituted Secondary and Tertiary Phosphine Oxides
Li, Shi-Guang,Yuan, Minglei,Topic, Filip,Han, Zhengxu S.,Senanayake, Chris H.,Tsantrizos, Youla S.
, p. 7291 - 7302 (2019)
An asymmetric synthesis, amenable to library preparation of structurally diverse P-chiral t-butyl substituted secondary phosphine oxides (SPOs) and tertiary phosphine oxides (TPOs), was developed. A P-chiral H-phosphinate building block was prepared via a two-step, one-pot condensation of a chiral auxiliary with t-BuPCl2, followed by hydrolysis. Nucleophilic displacement of the chiral auxiliary with Grignard reagents, followed by hydrolysis, provided a library of P-chiral SPOs. In situ treatment of the prehydrolysis intermediate with electrophiles also provided a library of P-chiral TPOs in high enantiomeric purity.
Palladium/Xiao-Phos-Catalyzed Kinetic Resolution of sec-Phosphine Oxides by P-Benzylation
Dai, Qiang,Liu, Lu,Zhang, Junliang
supporting information, p. 27247 - 27252 (2021/11/17)
P-stereogenic tert- and sec-phosphines have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, however, their practical synthesis still constitutes a significant challenge. Herein, a successful kinetic resolution of rac-se
Method for simultaneously synthesizing phosphine chiral center second-level/third-level phosphine oxide compound under catalysis of palladium/chiral ligand
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Paragraph 0040-0049, (2022/01/10)
The invention discloses a method for simultaneously synthesizing phosphine chiral center second-level/third-level phosphine oxide compounds under catalysis of palladium/chiral ligands. The method comprises the following steps: in the presence of an organic solvent and an additive, carrying out kinetic resolution reaction on racemic secondary phosphine oxide as shown in a formula I and an alkylating reagent as shown in a formula II under the catalysis of a palladium catalyst/chiral ligand Xiao-Phos to obtain phosphine chiral center secondary phosphine oxide as shown in a formula III and a phosphine chiral center tertiary phosphine oxide compound as shown in a formula IV, wherein a reaction formula is shown as a formula (a). The raw materials are stable and easy to obtain, the method is simple, and the substrate application range is wide. According to the invention, an efficient route with atom economy is provided for kinetic resolution of racemic secondary phosphine oxide and preparation of a phosphine chiral center compound, the follow-up synthesis application of the two products with high optical activity is expanded, and the synthetic method provided by the invention has very high practical application value.
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.
supporting information, 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
Bulky, optically active P-stereogenic phosphine-boranes from pure H-menthylphosphinates
Gatineau, David,Giordano, Laurent,Buono, Gerard
supporting information; experimental part, p. 10728 - 10731 (2011/09/14)
The transformation of readily available pure-H-menthylphosphinates into chiral phosphinous acid-boranes permits the elaboration of bulky P-stereogenic secondary phosphine-boranes. Taking advantage of the synthetic potential of these compounds, a broad range of hindered P-chiral tertiary phosphine-boranes has been prepared with excellent enantiomeric excesses. The utility of bulky o-tolylphosphines was illustrated by the synthesis of a rare enantiopure phosphapalladacycle (SP,SP)-12.
