565232-59-9Relevant academic research and scientific papers
Substituent Effects on the Structures of Alkali Metal Phosphido-Borane Complexes
Craig, Alex,Izod, Keith,Madlool, Atheer M.,Waddell, Paul G.
, (2022/04/19)
Metalation of tBu2PH(BH3) (1H), iPr2PH(BH3) (2H), iPrPhPH(BH3) (3H), Ph2PH(BH3) (4H) or (Mes)2PH(BH3) (5H) with one equivalent of nBuLi in either diethyl ether or THF gave the corresponding phosphido-borane complexes, which were obtained as single crystals of the solvates [{tBu2P(BH3)}Li(OEt2)]∞ (1Li), [{iPr2P(BH3)}Li(THF)2]∞ (2Li), [{iPrPhP(BH3)}Li(OEt2)2]∞ (3Li), [{Ph2P(BH3)}Li(OEt2)2]∞ (4Li), and [{(Mes)2P(BH3)}Li(THF)2]2 (5Li) after crystallization from diethyl ether; the alternative adduct [{Ph2P(BH3)}Li(TMEDA)]∞ (4Li(TMEDA)) was isolated from the reaction of 4Li with TMEDA. Similar metalation reactions between 1H, 2H or 4H and PhCH2Na gave the complexes [{tBu2P(BH3)}Na(THF)]∞ (1Na) and [{iPr2P(BH3)}Na(THF)]∞ (2Na), and [{Ph2P(BH3)}Na(TMEDA)(THF)]∞ (4Na(TMEDA)). Compounds 1Li, 2Li, 3Li, 4Li and 4Li(TMEDA) crystallize as zig-zag polymers, while 5Li crystallizes as a centrosymmetric dimer; compounds 1Na and 2Na crystallize as ribbon polymers, although these differ significantly in structure, while 4Na(TMEDA) crystallizes as a zig-zag polymer.
P-CHIROGENIC ORGANOPHOSPHORUS COMPOUNDS
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Page/Page column 31; 32; 33, (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.
Novel P-stereogenic PCP pincer-aryl ruthenium(II) complexes and their use in the asymmetric hydrogen transfer reaction of acetophenone
Medici, Serenella,Gagliardo, Marcella,Williams, Scott B.,Chase, Preston A.,Gladiali, Serafino,Lutz, Martin,Spek, Anthony L.,Van Klink, Gerard P.M.,Van Koten, Gerard
, p. 694 - 705 (2007/10/03)
Achiral P-donor pincer-aryl ruthenium complexes ([RuCl(PCP)(PPh 3)]) 4c,d were synthesized via transcyclometalation reactions by mixing equivalent amounts of [1,3-phenylenebis(methylene)] bis[diisopropylphosphine] (2c) or [1,3-phenylenebis(methylene)] bis[diphenylphosphine] (2d) and the N-donor pincer-aryl complex [RuCl{2,6-(Me2NCH2)2C6H 3}(PPh3)], (3; Scheme 2). The same synthetic procedure was successfully applied for the preparation of novel chiral P-donor pincer-aryl ruthenium complexes [RuCl(P*CP*)(PPh3)] 4a,b by reacting P-stereogenic pincer-arenes (S,S)-[1,3-phenylenebis(methylene)]bis[(alkyl) (phenyl)phosphines] 2a,b (alkyl = iPr or tBu, P*CHP*) and the complex [RuCl{2,6-(Me2NCH 2)2C6H3}(PPh3)], (3; Scheme 3). The crystal structures of achiral [RuCl(iPr,iPrPCP) (PPh3)] 4c and of chiral (S,S)-[RuCl-(tBu,PhPCP)(PPh 3)] 4a were determined by X-ray diffraction (Fig. 3). Achiral [RuCl(PCP)(PPh3)] complexes and chiral [RuCl(P*CP*) (PPh3)] complexes were tested as catalyst in the H-transfer reduction of acetophenone with propan-2-ol. With the chiral complexes, a modest enantioselectivity was obtained.
