13303-61-2Relevant academic research and scientific papers
Synthesis, Structure, and Solution Studies of Lithiated Allylic Phosphines and Phosphine Oxides
Eren, Nimrod M.,Orr, Samantha A.,Thompson, Christopher D.,Border, Emily C.,Stevens, Michael A.,Blair, Victoria L.
supporting information, p. 2080 - 2090 (2020/06/05)
This study reports a new series of 12 α-lithiated allylic phosphines and phosphine oxides. By incorporating Lewis base donors including diethyl ether (Et2O), tetrahydrofuran (THF), N,N,N′,N′,-tetramethylethylenediamine (TMEDA), and N,N,N′,N′,N″,-pentamethyldiethylenetriamine (PMDETA), nine complexes were structurally characterized by single-crystal X-ray crystallography. This includes novel dilithiated allylic phosphine 4 [PhP{CHCHCH2Li(TMEDA)}2] and a rare hemisolvated lithiated phosphine oxide 6 [{Ph2P(O)CHC(Me)CH2Li}2(TMEDA)]. Interestingly, in the solid state, P(III) complexes take advantage of Li-πinteractions to the newly formed delocalized system, in comparison to P(V) complexes where the oxophillic nature of the lithium atom dominates. All 12 complexes were fully characterized in the solution state by multinuclear NMR spectroscopy. DFT calculations on isomers of monomeric lithiated complex 3 [Ph2PCHC(Me)CH2Li(PMDETA)] described the low energy barrier between transition steps of the subtle delocalization of the allylic chain.
Enantioselective Coupling of Dienes and Phosphine Oxides
Nie, Shao-Zhen,Davison, Ryan T.,Dong, Vy M.
supporting information, p. 16450 - 16454 (2018/12/11)
We report a Pd-catalyzed intermolecular hydrophosphinylation of 1,3-dienes to afford chiral allylic phosphine oxides. Commodity dienes and air stable phosphine oxides couple to generate organophosphorus building blocks with high enantio- and regiocontrol. This method constitutes the first asymmetric hydrophosphinylation of dienes.
Dearylation of arylphosphine oxides using a sodium hydride-iodide composite
Tejo, Ciputra,Pang, Jia Hao,Ong, Derek Yiren,Oi, Miku,Uchiyama, Masanobu,Takita, Ryo,Chiba, Shunsuke
supporting information, p. 1782 - 1785 (2018/02/21)
A new protocol for the dearylation of arylphosphine oxides was developed using sodium hydride (NaH) in the presence of lithium iodide (LiI). The transient sodium phosphinite could be functionalized with a range of electrophiles in a one-pot fashion.
Selective reduction of allenyl(diphenyl)phosphine oxides to allyl(diphenyl)phosphine oxides
Lozovskiy,Aleksandrova,Vasilyev
, p. 995 - 998 (2017/09/07)
The reduction of allenyl(diphenyl)phosphine oxides with HSiCl3 or LiAlH4 selectively afforded the corresponding allyl(diphenyl)phosphine oxides. 3-Methylbut-2-en-1-yl(diphenyl)phosphine oxide reacted with AlCl3 to give a m
Intermolecular hydrophosphination of alkynes and related carbon-carbon multiple bonds catalyzed by organoytterbiums
Takaki, Ken,Koshoji, Go,Komeyama, Kimihiro,Takeda, Mitsuhiro,Shishido, Tetsuya,Kitani, Akira,Takehira, Katsuomi
, p. 6554 - 6565 (2007/10/03)
Intermolecular hydrophosphination of alkynes with diphenylphosphine is catalyzed by a Yb - imine complex, [Yb(η2-Ph 2CNPh)(hmpa)3], to give alkenylphosphines and phosphine oxides after oxidative workup in good yields under
Synthesis of lanthanide(II)-imine complexes and their use in carbon-carbon and carbon-nitrogen unsaturated bond transformation
Takaki, Ken,Komeyama, Kimihiro,Takehira, Katsuomi
, p. 10381 - 10395 (2007/10/03)
Ytterbium and samarium metals reduced aromatic ketimines to give directly divalent azalanthanacyclopropane complexes 1 quantitatively, the structure of which was characterized by X-ray analysis. The imine complexes 1 catalyzed dehydrogenative silylation of terminal alkynes, hydrosilylation of imines and alkenes, and intermolecular hydrophosphination of alkynes. Moreover, dehydrogenative double silylation of conjugated dienes was achieved with 1.
Intermolecular hydrophosphination of alkynes and related carbon-carbon multiple bonds catalyzed by ytterbium-imine complexes
Takaki, Ken,Takeda, Mitsuhiro,Koshoji, Go,Shishido, Tetsuya,Takehira, Katsuomi
, p. 6357 - 6360 (2007/10/03)
Catalytic intermolecular hydrophosphination of alkynes with Ph2PH has been achieved by using a ytterbium-imine complex, [Yb(η2-Ph2CNPh)(hmpa)6]. Thus, both terminal and internal alkynes were converted in high yi
Quaternary ammonium salts as alkylating agents in the synthesis of tertiary phosphine oxides
Zalinyan, S. A.,Khachatryan, R. A.,Indzhikyan, M. H.
, p. 388 - 390 (2007/10/03)
A procedure was developed for the synthesis of tertiary phosphine oxides by alkylation of secondary phosphine oxides with quaternary ammonium salts.
Stereochemistry of direct olefin formation from carbonyl compounds and lithiated heterocyclic sulfones
Baudin, J. B.,Hareau, G.,Julia, S. A.,Lorne, R.,Ruel, O.
, p. 856 - 878 (2007/10/02)
The conditions for the title reaction were studied for the 2-benzothiazole and 2-pyridine series and for some examples in the 2-pyrimidine series.The olefin preparations were generally observed to be more efficient for 2-BT-sulfone systems.From the data of the hundred cases studied, it can be concluded that (E)-olefins are obtained: (i) from saturated BT-sulfones and aromatic aldehydes; and (ii) from benzylic BT-sulfones and branched saturated aldehydes (isobutyraldehyde, pivalaldehyde) or α,β-ethylenic or aromatic aldehydes. (Z)-olefins arise: (i) fom propargylic BT-sulfones and saturated or aromatic aldehydes; and (ii) from allylic or benzylic Pyr-sulfones and saturated aldehydes.Possible mechanisms for this new olefination procedure were examined. - heteroaromatic sulfones, organolithium derivatives, intramolecular ipso reactions, stereochemistry, elimination, olefination.
