43077-31-2Relevant academic research and scientific papers
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.
Nucleophilic substitution of p-stereogenic chlorophosphines: Mechanism, stereochemistry, and stereoselective conversions of diastereomeric secondary phosphine oxides to tertiary phosphines
Ye, Jing-Jing,Nie, Shao-Zhen,Wang, Ji-Ping,Wen, Jing-Hong,Zhang, Yu,Qiu, Mao-Ran,Zhao, Chang-Qiu
, p. 5384 - 5387 (2017/11/07)
A diastereomeric mixture of secondary phosphine oxide is stereospecifically converted to chlorophosphine salt by treatment with oxalyl chloride, which stereoselectively affords P-inverted or retained tertiary phosphines, depending on the substitution with aliphatic or aromatic Grignard reagents, respectively, in high to 99% yield and 99:1 dr. The repulsion of π- electron on aryl to lone electron pair on phosphorus is proposed for the P-retained substitution.
Resolution of a planar-chiral platinum(II) complex. Crystal and molecular structure of [SP-4-2-A]-(+)589-[PtCl(achiraphos)(R-PMenPh2)]PF 6 [achiraphos = (R*,S*)-2,3-bis(diphenylphosphino)butane; R-PMenPh2 = [1(R)-(1α,2β,5α)]-diphenylmenthylphosphine]
Gugger, Paul,Limmer, Stephan O.,Watson, Andrew A.,Willis, Anthony C.,Wild, S. Bruce
, p. 5692 - 5696 (2008/10/08)
The new meso ligand (R*,S*)-2,3-bis(diphenylphosphino)butane (achiraphos) has been synthesized and used to prepare the prochiral square-planar meso complex [PtCl2(achiraphos)]. Displacement of one or the other of the enantiotopic chlorine atoms in the complex with [1R-(1α,2β,5α)]-diphenylmenthylphosphine (R-PMenPh2), and subsequent treatment of the intermediate salts with ammonium hexafluorophosphate, affords the diastereomeric complexes [SP-4-2-A]- and [SP-4-3-C]-[PtCl(achiraphos)(R-PMenPh2)]PF6, which are epimeric at planar-chiral platinum(II). The homochiral SP-4-2-A epimer, C50H57ClF6P4Pt, [α]589 +22.4° (c 0.85, acetone), crystallizes in the orthorhombic space group P212121 with a = 9.900(3) A?, b = 15.559(4) A?, c = 32.789(10) A?, Z = 4, R = 0.036, and Rw = 0.042 for 3805 unique data having I > 3σ(I). The geometry around the platinum atom in the complex is square-planar with the R-PMenPh2 ligand situated trans to the diphenylphosphino group attached to the S carbon of the achiraphos. The optically pure complex is configurationally stable in solution in the absence of chloride.
PALLADIUM-CATALYZED ASYMMETRIC TELOMERIZATION OF ISOPRENE. PREPARATION OF OPTICALLY ACTIVE CITRONELLOL
Hidai, Masanobu,Mizuta, Haruyoshi,Yagi, Hiroshi,Nagai, Yozo,Hata, Kenji,Uchida, Yasuzu
, p. 89 - 98 (2007/10/02)
Palladium-catalyzed asymmetric telomerization of isoprene with methanol in the presence of optically active phosphorus ligands gave 1-methoxy-2,6-di-methyl-2,7-octadiene ('head-to-tail' methoxy telomer I) in an optically active form.This methoxy telomer I
CATALYTIC ASYMMETRIC HYDROSILYLATION OF OLEFINS. III. CHIRAL PHOSPHINE-PALLADIUM(II) COMPLEXES AS HYDROSILYLATION CATALYSTS
Yamamoto, Keiji,Kiso, Yoshihisa,Ito, Ryuichi,Tamao, Kohei,Kumada, Makoto
, p. 9 - 18 (2007/10/02)
A palladium(II) complex of menthyldiphenylphosphine (MDPP) or epimeric neomenthyldiphenylphosphine (NMDPP) was used as an effective catalyst for the asymmetric hydrosilylation of styrene and some cyclic conjugated dienes, such as cyclopentadiene; the reaction giving optically active 1-phenylethyl-silane and 2-cycloalkenylsilane derivatives, respectively.MDPP and NMDPP, as ligands which have configurations opposite to each other only at the chiral C(3) center adjacent to the diphenylphosphino group, gave enantiomeric (S)-(-)- and (R)-(+)-1-phenylethyltrichlorosilane, respectively, in the hydrosilylation of styrene with trichlorosilane.However, this is not the case for 2-cycloalkenylsilane formation.Intervention of a ?-allylic palladium is suggested to account for the observed enantioselectivity as well as regioselectivity in the palladium complex-catalyzed addition of trichlorosilane to these olefins.
