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Hazardous reagents in continuous-flow chemistry

Continuous-flow technology enables the use of hazardous reagents and the safe handling of hazardous intermediates. This chapter focuses on the application of continuous-flow techniques in reactions involving reactive organometallic reagents, hazardous nitrogenand halogen-based reagents, oxidants, and toxic low-molecular-weight reagents.

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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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Substitution, cage functionalization, and oxidation of the charge-compensated triruthenium monocarbollide cluster complex [1-SMe 2-2,2-(CO)2-7,11-(mu-H)2-2,7,11-{Ru 2(CO)6}-closo-2,1-RuCB10H8]

The compound [1-SMe2-2,2-(CO)2-7,11-(mu-H) 2-2,7,11-{Ru2(CO)6}-closo-2,1-RuCB 10H8] 1a reacts with PMe3 or PCy3 (Cy = cyclo-C6H11) to give the structurally different species [1-SMe2-2,2-(CO)2-7,11-(mu-H) 2-2,7,11-{Ru2(CO)5-(PMe3)}-closo-2, 1-RuCB10H8] 4 and [1-SMe2-2,2-(CO) 2-11-(mu-H)-2,7,11-{Ru2(mu-H)(CO)5(PCy 3)}-closo-2,1-RuCB10H8] 5, respectively. A symmetrically disubstituted product [1-SMe2-2,2-(CO) 2-7,11-(mu-H)2-2,7,11-{Ru2(CO) 4(PMe3)2}-closo-2,1-RuCB10H 8] 6 is obtained using an excess of PMe3. In contrast, the chelating diphosphines 1,1?-(PPh2)2-Fe(eta-C 5H4)2 and 1,2-(PPh2) 2-closo-1,2-C2B10H10 react with 1a to yield oxidative-insertion species [1-SMe2-2,2-(CO) 2-11-(mu-H)-2,7,11-{Ru2(mu-H)(mu-[1?,1?- (PPh2)2-Fe(eta-C5H4) 2])(CO)4}-closo-2,1-RuCB10H8] 7 and [1-SMe2-2,2-(CO)2-11-(mu-H)-2,7,11-{Ru 2(mu-H)(CO)4(1?-2?-(PPh2) 2-closo-1?,2?-C2B10H 10)}-closo-2,1-RuCB10H8] 8, respectively. In toluene at reflux temperatures, 1a with ButSSBut gives [1-SMe2-2,2-(CO)2-7-(mu-SBut)-11-(mu-H)-2, 7,11-{Ru2(mu-H)(mu-SBut)(CO)4}-closo-2,1- RuCB10H8] 9, and with ButC?CH gives [1-SMe2-2,2-(CO)2-7-{mu:eta2-(E)-CH=C(H) But}-11-{mu:eta2-(E)-CH=C(H)But}-2,7,11- {Ru2(CO)5}-closo-2,1-RuCB10H8] 10. In the latter, two alkyne groups have inserted into cage B-H groups, with one of the resulting B-vinyl moieties involved in a C-H…Ru agostic bond. Oxidation of 1a with I2 or HgCl2 affords the mononuclear ruthenium complex [1-SMe2-2,2,2-(CO)3-closo-2,1-RuCB 10H10] 11. The Roysl Society of Chemistry 2005.

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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 reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2. In a Article,once mentioned of 161265-03-8, Safety of (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

Co-catalysis over a bi-functional ligand-based Pd-catalyst for tandem bis-alkoxycarbonylation of terminal alkynes

A bi-functional ligand (L1) containing a diphosphino fragment and sulfonic acid group (-SO3H) enabled PdCl2(MeCN)2 to efficiently catalyze the tandem bis-alkoxycarbonylation of terminal alkynes to produce aryl-/alkyl-substituted succinate (alpha,omega-diesters). It was found that the -SO3H incorporated in L1 indispensably assisted the Pd-catalyst in accomplishing this tandem reaction via intramolecular synergic effects. Co-catalysis over the L1-based Pd-catalyst was not due to the physical mixture of Xantphos and MeSO3H. In situ FTIR analysis verified that the formation and stability of Pd-H active species were facilitated by the presence of L1. The formation of stabilized diacylpalladium intermediate (F) was the critical driving force for the second-step methoxycarbonylation. DFT calculation was carried out to optimize the geometric structure of F, which indicated that the developed intramolecular O?H hydrogen bonds were an important structural feature to stabilize F. In addition, the L1-based Pd-catalyst could be recycled successfully for at least 3 runs in the ionic liquid [Bmim]NTf2 without obvious activity loss and detectable metal leaching.

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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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Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.Application In Synthesis of 1,1-Bis(diphenylphosphino)ferrocene, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 12150-46-8, in my other articles.

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. 12150-46-8, Name is 1,1-Bis(diphenylphosphino)ferrocene, molecular formula is C34H28FeP2. In a Article,once mentioned of 12150-46-8, Application In Synthesis of 1,1-Bis(diphenylphosphino)ferrocene

Mechanistic studies of the palladium-catalyzed ring opening of oxabicyclic alkenes with dialkylzinc

The mechanism of the palladium-catalyzed ring opening of oxabicyclic alkenes with dialkylzinc has been studied. Experiments which rule out a pi-allyl mechanism were carried out. Trapping carbometalated products and synthesis and successful reaction of alkyl palladium species provided strong evidence in favor of an enantioselective carbopalladation as the key step in the mechanism. The studies also suggest that a cationic palladium species is responsible for carbopalladation of the alkene. The combination of palladium and dialkylzinc is unique in that the dialkylzinc functions both in the transmetalation to palladium and as a Lewis acid in forming the reactive cationic palladium species.

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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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Preparation of Tri- and tetrasubstituted allenes via regioselective lateral metalation of benzylic (Trimethylsilyl)alkynes using TMPZnCl·LiCl

The zincation of various 1-(trimethylsilyl)-3-aryl-1-propynes with TMPZnCl·LiCl followed by a Pd-catalyzed coupling with aryl halides provides arylated allenes in 52-92% yield. Subsequent metalation with TMPZnCl·LiCl and cross-coupling with a second different aryl halide provides regioselectively tetrasubstituted allenes in 42-70% yield. This sequence can be performed in a one-pot procedure. DFT calculations and NMR studies support the formation of allenylzinc and propargyllithium intermediates starting from 1-(trimethylsilyl)-3-phenyl-1-propyne.

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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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Palladium(0)-tetracyanoethylene complexes of diphosphines and a dipyridine with large bite angles, and their crystal structures

Complexes of Pd(tcne) (tcne = tetracyanoethylene) containing bidentate ligands with large bite angles, bis<2-(diphenylphosphino)phenyl> ether (L1), 4,6-bis(diphenylphosphino)-10,10-dimethyl-10H-dibenzo<1,4>oxasiline (L2), 4,5-bis(diphenylphosphino)-2,8-dimethylphenoxathiine (L3), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (L4) and trans-5,6-bis(2-pyridyl)bicyclo<2.2.1>hept-2-ene (L6), were prepared and characterised.The compound 4,6-bis(diphenylphosphino)dibenzofuran (L5) did not form chelating palladium complexes, owing to its large natural bite angle of 138 degree.The crystal structures of L6, *2.5CH2Cl2 1, *4CH2Cl2 2, *2CH2Cl2 4 and 5 have been determined.The similarity of electronic effects induced by the free diphosphines was demonstrated by MOPAC calculations.The geometries of the ligands, however, were most accurately predicted by molecular mechanics (MM2) calculations for the diphosphines, and MNDO for L6.The largest P-Pd-P angle in the zerovalent palladium complexes was found to be 104.6 degree.A further increase in the natural bite angle of the ligand results in elongation of the Pd-P bond length in the complex rather than enlargement of the P-Pd-P bite angle.The ligand L6 assumed a bite angle of 99.5(2) degree in complex 5, which is considerably smaller than its calculated value of 117 degree.

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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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Silver(I) poly(1,2,3-benzotriazolyl)borate complexes containing mono- and bidentate phosphine coligands

New silver(I) derivatives [Ag{HnB(btz)4 – n}(PR 3)x] (n = 1 or 2, x ranging from 1 to 3), containing monodentate tertiary phosphines and anionic poly(benzotriazol-1-yl)borates, have been prepared from the reaction of AgNO3 with PR3 (R = Ph, o-tolyl, m-tolyl, p-tolyl, Bns) and K[H2B(btz)2], or K[HB(btz)3] (Hbtz = 1,2,3-benzotriazole). When the reaction between K[H2B(btz)2] and AgNO3 was carried out in the presence of dppe (1,2-bis(diphenylphosphino)ethane), or dppf (1,1?-bis(diphenylphosphino)ferrocene), compounds [Ag{H 2B(btz)2}]2(L) (L = dppe or dppf) formed, the diphosphine acting as a bidentate bridging P2-donor. Solid state and solution properties of all complexes have been investigated through analytical and spectroscopic measurements (IR, 1H, 31P NMR), the 1H and 31P NMR spectra being interpreted in terms of equilibria that involve mono- and di-nuclear complexes. Adducts [Ag{HB(btz) 3}(PPh3)3] ? (1/2H2O) and [Ag{H2B(btz)2}]2 (dppf) have been characterised by single crystal X-ray studies. In the former, the HB(btz)3 is unidentate in an NAgP3 coordination environment; the latter is a dimer, the dppf bridging the two silver atoms, while the H2B(btz) 2 ligand, which chelates one silver, bridges to the second also, the array having 2-symmetry.

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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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Synthetic Route of 161265-03-8, Chemistry can be defined as the study of matter and the changes it undergoes. You’ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.161265-03-8, Name is (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), molecular formula is C39H32OP2. In a patent, introducing its new discovery.

Vicinal Diboration of Alkyl Bromides via Tandem Catalysis

Vicinal diboration of alkyl bromides via tandem catalysis is reported. The reported reaction exhibits a broad substrate scope, good functional group compatibility, and regioselectivity. Moreover, it shows good practicality due to the easy accessibility of alkyl bromides in combination with diverse transformations of diboronates. Mechanism study indicates that terminal alkenes are generated selectively through nickel-catalyzed dehydrohalogenation of alkyl bromides followed by base/MeOH promoted diboration process to provide 1,2-diboration products.

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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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Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn’t involve a screen. 166330-10-5, C36H28OP2. A document type is Article, introducing its new discovery., Computed Properties of C36H28OP2

Cu Photoredox Catalysts Supported by a 4,6-Disubstituted 2,2?-Bipyridine Ligand: Application in Chlorotrifluoromethylation of Alkenes

Interest in base metal catalysis motivates the development of Cu-based photoredox catalysts for organic synthesis. However, only a few Cu catalysts have been applied in photoredox reactions, the majority of which contain one or two 1,10-phenanthroline ligands. Here we design a 4,6-disubstituted 2,2?-bipyridine ligand for Cu. Two heteroleptic [Cu(N^N)(P^P)][PF6] complexes, where N^N stands for the 2,2?-bipyridine ligand and P^P stands for a bisphosphine ligand, have been synthesized and characterized. They exhibit longer excited state lifetimes and higher Cu(I)/Cu(II) potentials compared to the most widely used Cu catalyst, [Cu(dap)2]Cl. The complex with Xantphos as the P^P ligand is an efficient catalyst for chlorotrifluoromethylation of terminal alkenes, especially styrenes, which had been challenging substrates for previously reported photoredox reactions. This chlorotrifluoromethylation method enables the convenient introduction of a trifluoromethyl group into organic molecules under mild conditions, which is important for medicinal chemistry.

Interested yet? Keep reading other articles of 166330-10-5!, Computed Properties of C36H28OP2

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 is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 12150-46-8, Name is 1,1-Bis(diphenylphosphino)ferrocene, Safety of 1,1-Bis(diphenylphosphino)ferrocene.

BACE INHIBITORS

The present invention provides a compound of Formula III: wherein A is: and Z, R1, R2, R3, and R4 are as defined herein, or a pharmaceutically acceptable salt thereof.

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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