127686-75-3Relevant academic research and scientific papers
Reactivity of allyl anions of allylphosphine-boranes towards electrophiles
Stankevic, Marek,Siek, Marcin,Pietrusiewicz, K. Michal
, p. 102 - 126 (2011/06/20)
The reactivity of mesomeric carbanions derived from allylphosphine-boranes varies as a function of electrophile. Small sp3-electrophiles react predominantly at the α carbon atom whereas bulky sp3- electrophiles and carbonyl compounds react mainly at the γ carbon. In the case of electron-deficient aldehydes reduction of carbonyl group and formation of the corresponding alcohols is observed. This is attributed to the weakly reducing properties of carbanions derived from allylphosphine-boranes, whose mesomeric form resembles the structure of a modified borohydride. ARKAT-USA, Inc.
Homometathesis and cross-metathesis coupling of phosphine-borane templates with electron-rich and electron-poor olefins
Dunne, Katherine S.,Lee, Sarah E.,Gouverneur, Véronique
, p. 5246 - 5259 (2007/10/03)
Ruthenium-catalysed olefin cross-metathesis can be used to synthesise structurally diverse acyclic phosphines protected as their borane complexes. Homodimerisations have been investigated and proved successful only for the allyl-substituted borane-protected phosphines. In the presence of various olefinic partners, allyl-substituted P templates reacted in cross-couplings to give predominantly the E products but traces of the Z isomers were always detected in the crude reaction mixtures. In contrast, cross-metathesis of vinyl-substituted phosphine boranes took place with exclusive E-selectivity. Although the conversions were consistently very good to excellent, the yields of purified products were often significantly lower suggesting that some of the newly formed compounds are prone to decompose upon purification.
Reactivity of BH3 and 9-BBN towards palladium(II) complexes of diphenylvinyl- and diphenylallyl-phosphine; X-ray structures of [PdCl2(PPh2CH2CH2CH 3)]2 and [PdCl2(PPh<
Coles, Simon J.,Faulds, Paul,Hursthouse, Michael B.,Kelly, David G.,Ranger, Georgia C.,Toner, Andrew J.,Walker, Neil M.
, p. 234 - 240 (2007/10/03)
Palladium(II) chloride complexes PdCl2L2 and [PdCl2L]2 have been prepared with the phosphine ligands PPh2CH=CH2 and PPh2CH2CH=CH2. The reactions of PdClsub
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.
