127686-62-8Relevant academic research and scientific papers
Reduction of Tertiary Phosphine Oxides by BH 3 Assisted by Neighboring Activating Groups
Sowa, Sylwia,Stankevi?, Marek,Flis, Anna,Pietrusiewicz, K. Micha?
, p. 2106 - 2118 (2018/02/28)
Tertiary sulfanylphosphine and aminoalkylphosphine oxides can be easily converted into the corresponding tertiary sulfanylphosphine- and aminoalkylphosphine-boranes, respectively, through the facile P=O bond reduction by borane complexes. The easy reduction of the strong P=O bond by BH 3, a mild reducing agent, has been achieved through an intramolecular P=O - B complexation directed by proximal SH or NH activating groups located at the α- or β-position to the P=O bond. A generalized reduction mechanism has been proposed.
P-CHIROGENIC ORGANOPHOSPHORUS COMPOUNDS
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Page/Page column 31; 32, (2013/03/26)
The present invention relates to novel P-chirogenic organophosphorus compounds of general formula (I). The present invention also provides a process for the synthesis of said compounds of formula (I). The present invention also relates to intermediate products of general formulae (II), (III) and (IV), as shown below, which are involved in the synthesis of compounds (I). Further, the invention relates to metal complexes comprising compounds (I) as ligands. The novel compounds and complexes of the present invention are useful in asymmetric catalysis by transition metal complexes or organocatalysis, especially for asymmetric hydrogenation or allylation. Compounds of general formula (I) may useful as agrochemical and therapeutic substances, or as reagents or intermediates for fine chemistry.
A straightforward synthesis of unsymmetrical secondary phosphine boranes
Petit, Christelle,Favre-Reguillon, Alain,Mignani, Gerard,Lemaire, Marc
, p. 326 - 330 (2011/03/18)
A one-pot procedure for the synthesis of unsymmetrical alkyl-substituted secondary phosphine oxides is described. The sequential addition of N-benzylaniline to a solution of dichlorophenylphosphine and 1-methylimidazole in methylcyclohexane, separating of the protic ionic liquid formed, addition of Grignard reagent followed by hydrolysis gave unsymmetrical secondary phosphine oxides (SPOs) in high yield. The use of ionic liquids in the first step is essential and streamlined the synthesis. Unsymmetrical SPOs could be quantitatively reduced to secondary phosphine using a catalytic amount of Ti(OiPr)4 and tetramethyldisiloxane (TMDS) under mild reaction conditions.
Synthesis and reactions of phosphine-boranes. Synthesis of new bidentate ligands with homochiral phosphine centers via optically pure phosphine-boranes
Imamoto, Tsuneo,Oshiki, Toshiyuki,Onozawa, Takashi,Kusumoto, Tetsuo,Sato, Kazuhiko
, p. 5244 - 5252 (2007/10/02)
Secondary and tertiary phosphine-boranes were synthesized in one-pot from phosphine oxides or substituted chlorophosphines without isolation of the intermediate phosphines. Phosphine-boranes having a methyl group were metalated with sec-butyllithium. The generated carbanions reacted with alkyl halides or carbonyl compounds to yield various phosphine-borane derivatives. The carbanions underwent copper(II)-promoted oxidative coupling without impairment of the borane functionality. Secondary phosphine-boranes reacted with alkyl halides, aldehydes, or α,β-unsaturated carbonyl compounds to give phosphine-borane derivatives having a functional group. The boranato group of phosphine-boranes was removed in a stereospecific manner with retention of configuration by treatment with a large excess of amine such as morpholine. A new route to bidentate ligands with homochiral phosphine centers has been explored by utilizing these characteristic reactivities of phosphine-boranes. Thus, optically pure (S,S)-1,2-bis(o-anisylphenylphosphino)ethane, (R,R)-1,2-bis(tert-butylphenyl-phosphino)ethane, and (S,S)-1,4-bis(o-anisylphenylphosphino)butane have been synthesized via phosphine-boranes.
