09/29/21 News Discovery of Bis(4-(trifluoromethyl)phenyl)phosphine oxide

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A series of C1-symmetric phosphine-phospholane ligands, 1-(disubstituted phosphino)-2-(phospholano)benzenes (5), which are called UCAPs, with an achiral phosphino group and a chiral phospholane which can be sterically and electrically adjustable, has been designed and synthesized. In the asymmetric hydrogenation of (Z)-N-benzoyl-1-phenylpropenamine (3), the stereorecognition abilities of the 5d – e-Rh catalysts which have a bulkier aryl substituent on the achiral phosphorus are superior to that observed with the DuPHOS-Rh catalyst. The effects of varying substituents on the achiral phosphorus atom are discussed.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

9/22 News Some scientific research about Bis(4-(trifluoromethyl)phenyl)phosphine oxide

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In the palladium-catalyzed asymmetric hydrosilylation of styrene with trichlorosilane, several chiral monophosphine ligands, (R)-2-diarylphosphino-1,1?-binaphthyls (2), were examined for their enantioselectivity. The highest enantioselectivity was observed in the reaction with (R)-2-bis[3,5-bis-(trifluoromethyl)phenyl]phosphino-1,1?-binaphthyl (2g) , which gave (S)-1-phenylethanol of 98% ee after oxidation of the hydrosilylation product.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

Sep 2021 News Can You Really Do Chemisty Experiments About Bis(4-(trifluoromethyl)phenyl)phosphine oxide

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We carried out a comprehensive study on the generality, scope, limitations, and mechanism of the palladium-catalyzed hydrophosphorylation of alkynes with P(O)-H compounds (i.e., H-phosphonates, H-phosphinates, secondary phosphine oxides, and hypophosphinic acid). For H-phosphonates, Pd/dppp was the best catalyst. Both aromatic and aliphatic alkynes, with a variety of functional groups, were applicable to produce the Markovnikov adducts in high yields with high regioselectivity. Aromatic alkynes showed higher reactivity than aliphatic alkynes. Terminal alkynes reacted faster than internal alkynes. Sterically crowded H-phosphonates disfavored the addition. For H-phosphinates and secondary phosphine oxides, Pd/dppe/Ph2P(O)OH was the catalyst of choice, which led to highly regioselective formation of the Markovnikov adducts. By using Pd(PPh3)4 as the catalyst, hypophosphinic acid added to terminal alkynes to give the corresponding Markovnikov adducts. Phosphinic acids, phosphonic acid, and its monoester were not applicable to this palladium-catalyzed hydrophosphorylation. Mechanistic studies showed that, with a terminal alkyne, (RO)2P(O)H reacted, like a Br°nsted acid, to selectively generate the alpha-alkenylpalladium intermediate via hydropalladation. On the other hand, Ph(RO)P(O)H and Ph2P(O)H gave a mixture of alpha- and beta-alkenylpalladium complexes. In the presence of Ph2P(O)OH, hydropalladation with this acid took place first to selectively generate the alpha-alkenylpalladium intermediate. A subsequent ligand exchange with a P(O)H compound gave the phosphorylpalladium intermediate which produced the Markovnikov adduct via reductive elimination. Related intermediates in the catalytic cycle were isolated and characterized.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The three-component reaction of p-quinone monoacetals, amines and diarylphosphine oxides is developed to afford m-(diarylphosphinyl)anilides in moderate to high yields. The reaction may proceed via a process involving phospha-nucleophilic addition to an iminoquinone acetal intermediate and/or carbonyl-amine condensation with a phosphinyl enone intermediate.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Pd-catalyzed asymmetric C-H bond activation for the synthesis of P-stereogenic dibenzophospholes was efficiently achieved via two types of catalytic systems. Chiral phosphoric amides/acids as ligands provided the products with up to 5:95 er, and (R)-segphos as ligand resulted in enantioselectivities of up to 98:2.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A new dimension for secondary phosphine oxide (SPOs) ligands is described in this article. Demonstrated on original pi-allylic nickel structures, these self-assembled complexes trigger catalytic hydrophosphinylation reactions. Addition of a Lewis acid B(C6F5)3 switches the reactivity towards migratory insertion and thus ethylene oligomerization through an unprecedented outer-sphere interaction with the coordinated SPO ligand. NMR experiments and X-ray analyses allowed for the observation of the formation of zwitterionic active species as well as their degradation pathway.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

Some scientific research about Bis(4-(trifluoromethyl)phenyl)phosphine oxide

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An efficient palladium-catalyzed asymmetric synthesis of axially chiral vinyl arenes from aryl bromides and hydrazones is reported. The products were easily oxidized to axially chiral biaryl compounds, and the phosphine oxides were readily reduced to phosphine ligands.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Several mononuclear ruthenium(iv) complexes with phosphinous acid ligands [RuCl2(eta3:eta3-C10H16)(PR2OH)] have been synthesized (78-86% yield) by treatment of the dimeric precursor [{RuCl(mu-Cl)(eta3:eta3-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) with 2 equivalents of different aromatic, heteroaromatic and aliphatic secondary phosphine oxides R2P(O)H. The compounds [RuCl2(eta3:eta3-C10H16)(PR2OH)] could also be prepared, in similar yields, by hydrolysis of the P-Cl bond in the corresponding chlorophosphine-Ru(iv) derivatives [RuCl2(eta3:eta3-C10H16)(PR2Cl)]. In addition to NMR and IR data, the X-ray crystal structures of representative examples are discussed. Moreover, the catalytic behaviour of complexes [RuCl2(eta3:eta3-C10H16)(PR2OH)] has been investigated for the selective hydration of organonitriles in water. The best results were achieved with the complex [RuCl2(eta3:eta3-C10H16)(PMe2OH)], which proved to be active under mild conditions (60 C), with low metal loadings (1 mol%), and showing good functional group tolerance.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Herein an efficient and direct copper-catalyzed coupling of oxazoline-containing aryl bromides with electron-deficient secondary phosphine oxides is reported. The resulting tertiary phosphine oxides can be reduced to prepare a range of PHOX ligands. The presented strategy is a useful alternative to known methods for constructing PHOX derivatives.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A Cu-catalyzed enantioselective ring-opening/oxidative phosphorylation reaction of cyclic diaryliodonium salts and diarylphosphine oxides in the presence of TEMPO was reported. 18O-Labeled experiments showed that the reaction proceeded via oxidation, followed by C-O bond formation. Furthermore, atropisomeric phosphine oxides were prepared via a t-BuLi-mediated P-transfer reaction. Computational studies elucidated that the phosphine oxide transfer was through a concerted C-P bond formation and P-O bond-dissociation process.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate