60324-11-0Relevant academic research and scientific papers
Alkylation of phosphinite/phosphonite-boranes via temporary protection of the P-H bond
Modzelewski, Kamil,Sowa, Sylwia
supporting information, p. 2410 - 2426 (2020/08/19)
A new alkylation protocol for the synthesis of tertiary phosphonite-/phosphinite-boranes is developed. P-Alkylation products are obtained exclusively in moderate to very good yields from easily accessible (1-hydroxy-1-methylethyl)/(1-hydroxy-1-cyclohexyl) phosphonite/phosphinite-boranes upon reaction with a variety of electrophiles under mild conditions. The methodology opens up new synthetic routes for organophosphorus chemistry and offers access to valuable alkyl phosphonite/phosphinite-boranes. In contrast to previously reported oxidative removal-substitution sequences for the preparation of optically active phosphinite-boranes, our protocol provides a one-step procedure that occurs without loss of stereochemical information at phosphorus. This new approach provides a rather advantageous protocol when compared to direct alkylation methods (which may undergo P-epimerization) and occurs in a stereoselective manner even at 0 °C.
Chemoselective Reduction of the P=O Bond in the Presence of P–O and P–N Bonds in Phosphonate and Phosphinate Derivatives
Sowa, Sylwia,Pietrusiewicz, K. Micha?
supporting information, p. 923 - 938 (2019/01/22)
Chemoselective reduction of the strong P=O bond in the presence of weaker P–O (ester) and P–N (amide) bonds in phosphonic acid derivatives has constituted an unresolved problem in organophosphorus chemistry for years. This long-standing problem is now solved for biologically relevant α-hydroxy and α-amino phosphonic as well as phosphinic acids esters and amides. The reduction of the P=O bond without concomitant scission of the ester and amide bonds is affected by use of BH3, a mild reducing agent, which affords the corresponding borane protected PIII phosphonite and phosphinite derivatives in one step. A mechanistic rationale is proposed for the role played by neighboring OH and NHR groups in facilitating the reduction, and for the observed chemo- and stereoselectivity. The reduction methodology described opens previously unavailable synthetic options in chemistry of α-functionalized phosphonic and phosphinic acids by offering a unique possibility for direct modifications of oxidation level of the P-center in these compounds.
Copper-catalyzed synthesis of α-hydroxy phosphonates from H-phosphonates and alcohols or ethers
Zhao, Zengxiang,Xue, Wanhua,Gao, Yuxing,Tang, Guo,Zhao, Yufen
supporting information, p. 713 - 716 (2013/05/09)
Easy PC: α-Hydroxy phosphonates were synthesized by copper/tert-butyl hydroperoxide (TBHP)-catalyzed oxidative addition reactions of H-phosphonates with alcohols or ethers. Diverse α-hydroxy phosphonates were obtained from substituted benzyl alcohols or alkyl alcohols and alkyl ethers in moderate to good yields. Copyright
The preparation of dialkyl 1-hydroxyalkylphosphonates in the reaction of trialkyl phosphites with oxonium salts derived from aldehydes or ketones
Goldeman, Waldemar,Soroka, Miroslaw
, p. 3019 - 3024 (2008/02/08)
The reaction of trialkyl phosphites with aldehydes or ketones in the presence of hydrogen chloride gives dialkyl 1-hydroxyalkylphosphonates via Arbusov-like reaction of oxonium salts derived from aldehydes or ketones. This reaction is a very convenient instant method for the preparation of dialkyl 1-hydroxyalkylphosphonates with a good yield as an alternative to the well-known Abramov reaction. Georg Thieme Verlag Stuttgart.
