163311-93-1Relevant articles and documents
Defying Stereotypes with Nanodiamonds: Stable Primary Diamondoid Phosphines
Moncea, Oana,Gunawan, Maria A.,Poinsot, Didier,Cattey, Hélène,Becker, Jonathan,Yurchenko, Raisa I.,Butova, Ekaterina D.,Hausmann, Heike,?ekutor, Marina,Fokin, Andrey A.,Hierso, Jean-Cyrille,Schreiner, Peter R.
, p. 8759 - 8769 (2016)
Direct unequal C-H bond difunctionalization of phosphorylated diamantane was achieved in high yield from the corresponding phosphonates. Reduction of the functionalized phosphonates provides access to novel primary and secondary alkyl/aryl diamantane phos
Ready Approach to Organophosphines from ArCl via Selective Cleavage of C-P Bonds by Sodium
Ye, Jingjing,Zhang, Jian-Qiu,Saga, Yuta,Onozawa, Shunya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
, p. 2682 - 2694 (2020/07/30)
The preparation, application, and reaction mechanism of sodium phosphide R2PNa and other alkali metal phosphides R2PM (M = Li and K) have been studied. R2PNa could be prepared, accurately and selectively, via the reactions of SD (sodium finely dispersed in mineral oil) with phosphinites R2POR′ and chlorophosphines R2PCl. R2PNa could also be prepared from triarylphosphines and diarylphosphines via the selective cleavage of C-P bonds. Na was superior to Li and K for these reactions. R2PNa reacted with a variety of ArCl to efficiently produce R2PAr. ArCl is superior to ArBr and ArI since they only gave low yields of the products. In addition, Ph2PNa is superior to Ph2PLi and Ph2PK since Ph2PLi did not produce the coupling product with PhCl, while Ph2PK only gave a low yield of the product. An electron-withdrawing group on the benzene ring of ArCl greatly accelerated the reactions with R2PNa, while an alkyl group reduced the reactivity. Vinyl chloride and alkyl chlorides RCl also reacted efficiently. While t-BuCl did not produce the corresponding product, admantyl halides could give the corresponding phosphine in high yields. A wide range of phosphines were prepared by this method from the corresponding chlorides. Unsymmetric phosphines could also be conveniently generated in one pot starting from Ph3P. Chiral phosphines were also obtained in good yields from the reactions of menthyl chlorides with R2PNa. Possible mechanistic pathways were given for the reductive cleavage of R3P by sodium generating R2PNa and the substitution reactions of R2PNa with ArCl generating R2PAr.
Reactions of 1- and 2-Halo and 1,2-Dichloroadamantanes with Nucleophiles by the SRN1 Mechanism
Santiago, Ana N.,Stahl, Adriana E.,Rodriguez, Gladis L.,Rossi, Roberto A.
, p. 4406 - 4411 (2007/10/03)
2-Bromoadamantane (2-BrAd) reacted in liquid ammonia under irradiation with diphenylphosphide (Ph2P-) ions whereas 2-chloroadamantane (2-ClAd) did not under the same experimental conditions. However, 2-ClAd yielded 2-(trimethylstannyl)adamantane in its photostimulated reaction with trimethylstannyl (Me3Sn-) ions. The compound 1-ClAd yielded the substitution product in a photostimulated slow reaction when the nucleophile is Ph2P- ion; the reaction occurs faster with the nucleophile Me3Sn- ion. All these reactions can be explained by the SRN1 mechanism as they did not occur in the dark and were inhibited by p-dinitrobenzene when photostimulated. In competition experiments, 1-haloadamantane showed more reactivity than 2-haloadamantane. Either with Ph2P- or Me3Sn- ions, 1-BrAd is 1.4 times more reactive than 2-BrAd while 1-ClAd is 12 times more reactive than 2-ClAd with Me3Sn- ions. In the photostimulated reaction of 1,2-dichloroadamantane (7) with Ph2P- the monosubstitution products 1-adamantyldiphenylphosphine (64%) and 2-adamantyldiphenylphosphine (15%) were formed, isolated as the oxides. From these results, it appears that when 7 receives an electron, the 1-position fragments ca. four times faster than the 2-position. The disubstitution product was not formed with Ph2P- ions, but when 7 reacted with a nucleophile having less steric bulk such as a Me3Sn- ion, the 2-chloro-1-(trimethylstannyl)-adamantane and the disubstitution product 1,2-bis(trimethylstannyl)adamantane were formed. The formation of these products is explained in terms of the different rates of the electron transfer reactions of the radical anion intermediates.
