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Mono-Phosphazenyl Phosphines (R2N)(3)P=N-P(NR2)(2) – Strong P-Bases, P-Donors, and P-Nucleophiles for the Construction of Chelates

We present a convenient three-step synthesis of amino substituted phosphazenyl phosphines of the general formula (R2N)(3)P=N-P(NR2)(2) [NR2 = N(CH2)(4), N(CH2)(5), N(CH2)(6)]. These easily accessible mixed valent compounds display a surprisingly high proton affinity and basicity in the same range as the corresponding Schwesinger diphosphazene (Me2N)(3)P=N-P=NEt(NMe2)(2) (Et-P-2) and Verkade’s proazaphosphatrane superbases. Within the central [P-III-N=P-V] scaffold, the phosphine P-III and not the phosphazene N-III atom is the center of highest proton affinity, basicity and donor strength. As P-bases, the title compounds display calculated proton affinities between 265.8 (NR2 = NMe2) and 274.7 kcal center dot mol(-1) [NR2 = N(CH2)(4)] and pK(BH)(+) values between 26.4 (NR2 = NMe2) and 31.5 [NR2 = N(CH2)(4)] on the acetonitrile scale. As P-nucleophiles, they are key intermediates in the synthesis of hyperbasic bis(diphosphazene) proton sponges, chiral bis(diphosphazene) proton pincers, bisphosphazides, and superbasic P-2-bisylides. Their Staudinger reactions as nucleophile towards 1,8-diazidonaphthalene leading to 1,8-naphthalene-bisphosphazides is described in detail. The donor strength of the title compounds towards fragments [Se] and [Ni(CO)(3)] is in the same range as that of N-heterocyclic carbenes.

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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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Chemistry of 1,2-diphospholide anions and 1,2-diphospholes

The main trends in the chemistry of 1,2-diphosphacyclopentadienes (1,2-diphospholes) and their derivatives 1,2-diphosphacyclopentadienide anions (1,2-diphospholide anions) were systematized, analyzed, and generalized. Methods for the generation of 1,2-diphospholide anions and their reactions with organic and organoelement electrophiles, as well as with transition metal complexes, were considered. Particular attention was paid to the cycloaddition reactions of 1-alkyl-1,2-diphospholes to obtain polycyclic chiral phosphines. A comparative analysis of the reactivity of 1,2-diphospholes and 1,2-diphospholide anions with respect to other representatives of phosphacyclopentadienes and phosphacyclopentadienide anions was carried out. The potential of application of 1,2-diphosphacyclopentadiene derivatives for the design of materials with magnetic, catalytic, and optical properties was shown.

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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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Strong chiroptical activity in Au(25)clusters protected by mixed ligands of chiral phosphine and achiral thiolate

We report the successful synthesis of a chiroptically active Au(25)cluster protected by mixed ligands of chiral bidentateS-BINAP and achiral dodecanethiol (DDT), which can be formulated as [Au-25(S-BINAP)(4)(DDT)(5)X-4] (X = Cl or Br). The UV-vis absorption spectral pattern is similar to that of the well-known bi-icosahedral cluster [Au-25(PPh3)(10)(SR)(5)X-2](2+), so the obtained cluster should also have a similar bi-icosahedral structure assembled from two vertex-sharing icosahedral Au(13)units. With a closer inspection of the optical absorption, interestingly, the lowest-energy peak is red-shifted as compared to that of [Au-25(PPh3)(10)(SR)(5)X-2](2+). Quantum chemical calculations for model bi-icosahedral Au(25)structures suggest the reason of the red shift. On the other hand, the obtained Au(25)cluster exhibits a weak CD signature in the lowest-energy transition region, whereas higher-energy transitions have very large chiroptical responses with a maximumg-factor of 1.7 x 10(-3). The calculations also give implications for the origin of the CD response in the Au(25)cluster. We then believe that bi-icosahedral Au(25)clusters with chirality will be a good prototype for understanding the influence of constituent Au(13)units on the chiroptical activity of their assembling structures.

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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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Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law. In my other articles, you can also check out more blogs about 18437-78-0. COA of Formula: C18H12F3P.

Chemistry is the experimental science by definition. We want to make observations to prove hypothesis. For this purpose, we perform experiments in the lab. , COA of Formula: C18H12F3P, 18437-78-0, Name is Tris(4-fluorophenyl)phosphine, molecular formula is C18H12F3P, belongs to chiral-phosphine-ligands compound. In a document, author is Wang, Kaiye, introduce the new discover.

Asymmetric kinetic resolution of sulfides for the construction of unsymmetric sulfides and chiral 3,3-disubstituted oxindoles

A range of 3,3-disubstituted oxindoles accessed using para-quinone methides derived from isatins with thiols were used for the formation of unsymmetrical disulfides, and 3,3-disubstituted oxindoles with a chiral quaternary carbon center and unsymmetric disulfides could also be directly obtained with high selectivities catalyzed by chiral phosphines in one step.

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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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Synthesis of alpha-Aminophosphines by Copper-Catalyzed Regioselective Hydroamination of Vinylphosphines

A copper-catalyzed net hydroamination of vinyl-phosphine boranes with hydrosilanes and O-benzoylhy-droxylamines has been developed. The reaction proceeds regioselectively to form the corresponding alpha-aminophosphine boranes of potent interest in medicinal and pharmaceutical chemistry. This copper catalysis is based on an umpolung, electrophilic amination strategy and provides a new electrophilic amination approach to alpha-aminophosphine derivatives. Additionally, although still preliminary, asymmetric synthesis has also been achieved by judicious choice of a chiral bisphosphine-ligated copper complex.

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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 catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 18437-78-0, Name is Tris(4-fluorophenyl)phosphine, molecular formula is C18H12F3P. In an article, author is Lin, Tao-Yan,once mentioned of 18437-78-0, COA of Formula: C18H12F3P.

Design and Synthesis of TY-Phos and Application in Palladium-Catalyzed Enantioselective Fluoroarylation ofgem-Difluoroalkenes

The first example of highly enantioselective fluoroarylation of gem-difluoroalkenes with aryl halides is presented by using a new chiral sulfinamide phosphine (Sadphos) type ligandTY-Phos. N-Me-TY-Phoscan be easily synthesized on a gram scale from readily available starting materials in three steps. Salient features of this work including readily available starting materials, good yields, high enantioselectivities as well as broad substrate scope make this approach very practical and attractive. Notably, the asymmetric synthesis of an analogue of a biologically active molecule is also reported.

Interested yet? Keep reading other articles of 18437-78-0, you can contact me at any time and look forward to more communication. COA of Formula: C18H12F3P.

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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Chemo-enzymatic cascade processes are invaluable due to their ability to rapidly construct high-value products from available feedstock chemicals in a one-pot relay manner. In an article, author is Zhang, Jinxia, once mentioned the application of 18437-78-0, Name is Tris(4-fluorophenyl)phosphine, molecular formula is C18H12F3P, molecular weight is 316.26, MDL number is MFCD00013553, category is chiral-phosphine-ligands. Now introduce a scientific discovery about this category, Recommanded Product: Tris(4-fluorophenyl)phosphine.

Chiral zinc amidate catalyzed additions of diethylzinc to aldehydes

A series of bifunctional Spiro ligands bearing carboxamide-phosphine oxide groups and ethylzinc carboxamidates from these ligands as catalysts for Et2Zn additions to aldehydes were reported. Excellent yields were obtained with moderate ee’s in Et2Zn additions to benzaldehyde derivatives, implying effectiveness of our newly designed catalytic structures as well as mediocre stereocontrol by these chiral ligands. Possible transition states were suggested based on the crystal structures of two ligands. (C) 2019 Elsevier Ltd. All rights reserved.

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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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Phosphorus-containing amino acids with a P-C bond in the side chain or a P-O, P-S or P-N bond: from synthesis to applications

Since the discovery of (l)-phosphinothricin in the year 1970, the development of alpha-amino acids bearing a phosphorus group has been of renewed interest due to their diverse applications, including their use in [F-18]-fluorolabeling, as fluorescent probes, as protecting groups and in the reversible immobilization of amino acids or peptide derivatives on carbon nanomaterials. Considerable progress has also been achieved in the field of antiviral agents, through the development of phosphoramidate prodrugs, which increase significantly the intracellular delivery of nucleoside monophosphate and monophosphonate analogues. This review aims to summarize the strategies reported in the literature for the synthesis of P(iii), P(iv) and P(v) phosphorus-containing amino acids with P-C, P-O, P-S or P-N bonds in the side chains and their related applications, including their use in natural products, ligands for asymmetric catalysis, peptidomimetics, therapeutic agents, chemical reagents, markers and nanomaterials. The discussion is organized according to the position of the phosphorus atom linkage to the amino acid side chain, either in an alpha-, beta-, gamma- or delta-position or to a hydroxyl, thiol or amino group.

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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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Application of 18437-78-0, The transformation of simple hydrocarbons into more complex and valuable products via catalytic C¨CH bond functionalisation has revolutionised modern synthetic chemistry. 18437-78-0, Name is Tris(4-fluorophenyl)phosphine, SMILES is FC1=CC=C(P(C2=CC=C(F)C=C2)C3=CC=C(F)C=C3)C=C1, belongs to chiral-phosphine-ligands compound. In a article, author is Koegel, Julius F., introduce new discover of the category.

Mono-Phosphazenyl Phosphines (R2N)(3)P=N-P(NR2)(2) – Strong P-Bases, P-Donors, and P-Nucleophiles for the Construction of Chelates

We present a convenient three-step synthesis of amino substituted phosphazenyl phosphines of the general formula (R2N)(3)P=N-P(NR2)(2) [NR2 = N(CH2)(4), N(CH2)(5), N(CH2)(6)]. These easily accessible mixed valent compounds display a surprisingly high proton affinity and basicity in the same range as the corresponding Schwesinger diphosphazene (Me2N)(3)P=N-P=NEt(NMe2)(2) (Et-P-2) and Verkade’s proazaphosphatrane superbases. Within the central [P-III-N=P-V] scaffold, the phosphine P-III and not the phosphazene N-III atom is the center of highest proton affinity, basicity and donor strength. As P-bases, the title compounds display calculated proton affinities between 265.8 (NR2 = NMe2) and 274.7 kcal center dot mol(-1) [NR2 = N(CH2)(4)] and pK(BH)(+) values between 26.4 (NR2 = NMe2) and 31.5 [NR2 = N(CH2)(4)] on the acetonitrile scale. As P-nucleophiles, they are key intermediates in the synthesis of hyperbasic bis(diphosphazene) proton sponges, chiral bis(diphosphazene) proton pincers, bisphosphazides, and superbasic P-2-bisylides. Their Staudinger reactions as nucleophile towards 1,8-diazidonaphthalene leading to 1,8-naphthalene-bisphosphazides is described in detail. The donor strength of the title compounds towards fragments [Se] and [Ni(CO)(3)] is in the same range as that of N-heterocyclic carbenes.

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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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Backdoor Induction of Chirality: Trans-1,2-cyclohexanediamine as Key Building Block for Asymmetric Hydrogenation Catalysts

This paper describes the synthesis and characterization of 21 chiral monodentate ligands L, assembled of three building blocks utilizing amide bonds: a metal binding triphenylphosphine, a chiral cyclic diamine and an additional substituent for fine-tuning the steric and/or electronic properties. Cis square-planar metal complexes of Rh-I and Pt-II with ML2 stoichiometry have been prepared and characterized by spectroscopic methods (NMR, IR, UV-Vis, CD) and DFT calculations. A key feature of the metal complexes is a prochiral metal coordination sphere and backdoor induction of chirality from a distant chiral source via an outer-coordination sphere, well-defined by aromatic stacking and hydrogen-bonding. The rhodium complexes were used as catalysts in asymmetric hydrogenation of alpha,beta-dehydroamino acids with excellent yield and selectivity (up to 97 % ee), strongly supporting the backdoor induction hypothesis.

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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