- Alkylation of phosphinite/phosphonite-boranes via temporary protection of the P-H bond
-
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.
- Modzelewski, Kamil,Sowa, Sylwia
-
-
Read Online
- New synthesis of trimethylsilyl esters of phosphorus(III) acids
-
Abstract: A novel synthetically important reaction has been developed for the quick, convenient, and high-yield preparation of trimethylsilyl esters of phosphorus(III) acids, synthetically valuable Michaelis–Arbuzov reaction precursors. Commercially and synthetically available initial compounds used are derivatives of propan-2-ol phosphorylated in the second position capable of long-term storage and available silylating reagents: hexamethyldisilazane, bis(trimethylsilyl)acetamide, and diethyl(trimethylsilyl)amine. Also, a stepwise reaction scheme of the starting compounds with silylating reagents has been proposed. Graphic abstract: [Figure not available: see fulltext.].
- Morgalyuk, Vasily,Strelkova, Tatyana,Brel, Valery
-
p. 1993 - 1997
(2019/11/13)
-
- Chemoselective Reduction of the P=O Bond in the Presence of P–O and P–N Bonds in Phosphonate and Phosphinate Derivatives
-
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.
- Sowa, Sylwia,Pietrusiewicz, K. Micha?
-
supporting information
p. 923 - 938
(2019/01/22)
-