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BICYCLIC AZAHETEROCYCLOBENZYLAMINES AS PI3K INHIBITORS

The present invention provides bicyclic azaheterocyclobenzylamines of Formula I: wherein the variables are defined herein, that modulate the activity of phosphoinositide 3-kinases (PI3Ks) and are useful in the treatment of diseases related to the activity of PI3Ks including, for example, inflammatory disorders, immune-based disorders, cancer, and other diseases

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Reference£º
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-Catalyzed Formal Insertion of Carbenoids into Aminals via C-N Bond Activation

A new strategy for selective insertion of metal carbenes into C-N bond has been developed via Pd-catalyzed C-N bond activation. A series of aminals and alpha-diazoesters with different substituents were successfully incorporated even in 0.1 mol % of catalyst under mild conditions, affording a wide range of alpha,beta-diamino acid esters with quarternary carbon-centers. Preliminary mechanistic studies uncovered that the unique electrophilic cyclopalladated species could easily react with diazoacetates to generate a Pd-carbenoid intermediate which was involved in the catalytic cycle.

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Reference£º
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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Mild Pd-catalyzed aminocarbonylation of (hetero)aryl bromides with a palladacycle precatalyst

A palladacyclic precatalyst is employed to cleanly generate a highly active XantPhos-ligated Pd-catalyst. Its use in low temperature aminocarbonylations of (hetero)aryl bromides provides access to a range of challenging products in good to excellent yields with low catalyst loading and only a slight excess of CO. Some products are unattainable by traditional carbonylative coupling.

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Reference£º
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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MONOCYCLIC OR BICYCLIC CARBOCYCLES AND HETEROCYCLES AS FACTOR XA INHIBITORS

The present application describes monocyclic or bicyclic carbocycles and heterocycles and derivatives thereof of Formula I: or pharmaceutically acceptable salt forms thereof, which are useful as inhibitors of factor Xa.

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Reference£º
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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Nitrogen-heterocyclic compound and process for production thereof

A nitrogen-heterocyclic compound is provided which is represented by General Formula (1): where R1 and R2 are independently hydrogen, an alkyl group, an aryl group, or a heteroaryl group; R3 is hydrogen or an aryl group; R4 is a substituted amino group, an alkoxy group, a nitro group, or halogen; m is an integer from 0 to 2; and n is 0 or 1. A process for producing the above compound is also provided. This compound is useful as a source material of medicines, pesticides, electronic materials, and intermediates for other substituted nitrogen-heterocyclic compounds.

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Reference£º
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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Ru(II) xantphos complex as an efficient catalyst in transfer hydrogenation of carbonyl compounds

In the transfer hydrogenation of aromatic/aliphatic carbonyl compounds using iso-propanol-potassium hydroxide mixture as hydrogen donor, a mixed ligand Ru(II) complex, prepared from xantphos ligand and RuCl2(dmso) 4, was examined. Besides, the solid state structure of the Ru (II) complex was determined using X-ray single crystallography. The catalytic reactivity of the complex was remarkable (up to 99%) and the catalyst showed more efficiency in the reduction of ketones than aldehydes.

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Reference£º
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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Improving the Catalytic Activity in the Rhodium-Mediated Hydroformylation of Styrene by a Bis(N-heterocyclic silylene) Ligand

For the first time, a significant boost in catalytic activity in the rhodium-catalysed hydroformylation of an alkene by using a bidentate bis(N-heterocyclic silylene) ligand is reported. This is shown by the hydroformylation of styrene at 30 bar CO/H2 pressure in the presence of [HRh(CO)(PPh3)3] with an excess of the ferrocenediyl-based bis-NHSi ligand 4, [({eta5-C5H4{PhC(NtBu)2}Si})2Fe], which results in superior catalytic activity, compared with the bidentate diphosphines DPPF (3a) and xantphos (3b). In contrast, the hydroformylation of styrene in the presence of [HRh(CO)(PPh3)3] with excesses of the monodentate NHSi ligands [{PhC(NtBu)2}SiNMe2] (1) and [{C2H2(NtBu)2}Si:] (2) at 30 bar CO/H2 pressure revealed considerably slower conversion to the aldehyde products than [HRh(CO)(PPh3)3], with or without an excess of PPh3, showing catalyst deactivation. Surprisingly, the germanium analogue of 4 is shown to be virtually catalytically inactive. The superior activity of 4, compared with the xantphos-containing benchmark system, is rationalized on the basis of solution NMR spectroscopic studies, and the comparative catalyst cycles are elucidated using density functional theory (DFT) methods. The latter quantum-chemical studies explain very well the favourable energy pathway for the hydroformylation of styrene using 4 versus xantphos.

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Reference£º
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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Heteroleptic Copper Photosensitizers: Why an Extended pi-System Does Not Automatically Lead to Enhanced Hydrogen Production

A series of heteroleptic copper(I) photosensitizers of the type [(P^P)Cu(N^N)]+with an extended pi-system in the backbone of the diimine ligand has been prepared. The structures of all complexes are completely characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography. These novel photosensitizers were assessed with respect to the photocatalytic reduction of protons in the presence of triethylamine and [Fe3(CO)12]. Although the solid-state structures and computational results show no significant impact of the pi-extension on the structural properties, decreased activities were observed. To explain this drop, a combination of electrochemical and photophysical measurements including time-resolved emission as well as transient absorption spectroscopy in the femto- to nanosecond time regime was used. Consequently, shortened excited state lifetimes caused by the rapid depopulation of the excited states located at the diimine ligand are identified as a major reason for the low photocatalytic performance.

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Reference£º
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 Routes to Thiol-Functionalized Organic Semiconductors for Molecular and Organic Electronics

Over the few last decades, the potential of using thiol functionalities to induce the self-assembly of various kinds of molecules on metal surfaces has been widely demonstrated. In particular, pi-conjugated molecules can undergo self-assembly on metallic surfaces to create electroactive supramolecular layers, which have found important applications in organic and molecular electronics. For this reason, the synthesis of thiol-functionalized conjugated molecules has been the object of extensive research and many routes have been developed for their synthesis. This Focus Review provides an overview of the state-of-the-art methods for the syntheses of organic semiconductors that are decorated with pendant thiol groups for applications in self-assembly and molecular and organic electronics. Particular attention is given to synthetic strategies based on organometallic cross-coupling reactions for the preparation of compounds with extended conjugation.

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Reference£º
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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High-yielding tandem hydroformylation/hydrogenation of a terminal olefin to produce a linear alcohol using a Rh/Ru dual catalyst system

(Chemical equation presented) A dual catalyst system has been developed for tandem hydroformylation/hydrogenation to produce n-undecanol from 1-decene in one pot. A combination of xantphos/[Rh(acac)(CO)2] and Shvo’s catalyst (1) afforded the best results (see scheme; acac = acetylacetonate, DMA = N,N-dimethylacetamide). Polar solvents effectively suppressed the formation of undecyl formate.

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Reference£º
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