100809-49-2Relevant articles and documents
Organocatalyzed Reduction of Tertiary Phosphine Oxides
Schirmer, Marie-Luis,Jopp, Stefan,Holz, Jens,Spannenberg, Anke,Werner, Thomas
supporting information, p. 26 - 29 (2016/01/25)
A novel selective catalytic reduction method of tertiary phosphine oxides to the corresponding phosphines has been developed. Notably, the reaction proceeds smoothly with low catalyst loadings of 1-5 mol% even at low temperature (70 C). Under the optimized conditions various phosphine oxides could be selectively reduced and the desired phosphines were usually obtained in excellent yields above 90%. Furthermore, we have developed a one-pot reaction sequence for the preparation of valuable phosphinborane adducts. Simple addition of BH3THF subsequent to the reduction step gave the desired adducts in yields up to 99%.
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.
