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Iridium-catalyzed diborylation of benzylic C-H bonds directed by a hydrosilyl group: Synthesis of 1,1-benzyldiboronate esters

We describe a regioselective diborylation of primary benzylic C-H bonds catalyzed by [Ir(COD)OMe]2 and 4,4?-di-tert-butyl-2,2?- bipyridine (dtbpy). The hydrosilyl group acts as a traceless directing group, providing access to a range of 1,1-benzyldiboronate esters in good yields. Transformations of the 1,1-benzyldiboronate ester products include chemoselective Suzuki-Miyaura cross-couplings and synthesis of tetrasubstituted alkenyl boronate esters.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Awesome and Easy Science Experiments about Bis(tri-tert-butylphosphine)palladium

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Discovery of 6-[5-(4-fluorophenyl)-3-methyl-pyrazol-4-yl]-benzoxazin-3-one derivatives as novel selective nonsteroidal mineralocorticoid receptor antagonists

In the course of our study on selective nonsteroidal mineralocorticoid receptor (MR) antagonists, a series of novel benzoxazine derivatives possessing an azole ring as the core scaffold was designed for the purpose of attenuating the partial agonistic activity of the previously reported dihydropyrrol-2-one derivatives. Screening of alternative azole rings identified 1,3-dimethyl pyrazole 6a as a lead compound with reduced partial agonistic activity. Subsequent replacement of the 1-methyl group of the pyrazole ring with larger lipophilic side chains or polar side chains targeting Arg817 and Gln776 increased MR binding activity while maintaining the agonistic response at the lower level. Among these compounds, 6-[1-(2,2-difluoro-3-hydroxypropyl)-5-(4-fluorophenyl)-3-methyl-1H-pyrazol-4-yl]-2H-1,4-benzoxazin-3(4H)-one (37a) showed highly potent in vitro activity, high selectivity versus other steroid hormone receptors, and good pharmacokinetic profiles. Oral administration of 37a in deoxycorticosterone acetate-salt hypertensive rats showed a significant blood pressure-lowering effect with no signs of antiandrogenic effects.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Awesome and Easy Science Experiments about Bis(tri-tert-butylphosphine)palladium

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A flexible, palladium-catalyzed indole and azaindole synthesis by direct annulation of chloroanilines and chloroaminopyridines with ketones

The “ringmaster” [Pd(tBu3P)2] serves as the catalyst in the direct synthesis of indoles by annulation of ortho-chloroanilines with ketones (see picture). This versatile method can be used to synthesize a variety of functionalized indoles and azaindoles. DMA = dimethylacetarnide.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Regio- and Stereoselective Synthesis of 1,1-Diborylalkenes via Br°nsted Base-Catalyzed Mixed Diboration of Alkynyl Esters and Amides with BpinBdan

The NaOtBu-catalyzed mixed 1,1-diboration of terminal alkynes using the unsymmetrical diboron reagent BpinBdan (pin = pinacolato; dan = 1,8-diaminonaphthalene) proceeds in a regio- and stereoselective fashion affording moderate to high yields of 1,1-diborylalkenes bearing orthogonal boron protecting groups. It is applicable to gram-scale synthesis without loss of yield or selectivity. The mixed 1,1-diborylalkene products can be utilized in Suzuki?Miyaura cross-coupling reactions which take place selectivly at the C?B site. DFT calculations suggest the NaOtBu-catalyzed mixed 1,1-diboration of alkynes occurs through deprotonation of the terminal alkyne, stepwise addition of BpinBdan to the terminal carbon followed by protonation with tBuOH. Experimentally observed selective formation of (Z)-diborylalkenes is supported by our theoretical studies.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Discovery of Bis(tri-tert-butylphosphine)palladium

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Synthesis of arylstannanes by palladium-catalyzed desulfitative coupling reaction of sodium arylsulfinates with distannanes

A novel Pd-catalyzed desulfitative cross-coupling reaction of sodium arylsulfinates with hexaalkyl distannanes is realized, allowing the facile synthesis of functionalized arylstannanes with moderate to excellent yields. The successful implement of gram-scale synthesis and tandem Stille coupling reaction demonstrates the potential applications of this method in organic synthesis.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Extracurricular laboratory:new discovery of Bis(tri-tert-butylphosphine)palladium

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INDOLINONE ANALOGUES

The present invention encompasses compounds of general formula (I) wherein the groups R1 to R4, A1 and A2 have the meanings given in the claims and in the specification. The compounds of the invention are suitable for the treatment of diseases characterized by excessive or abnormal cell proliferation pharmaceutical preparations containing such compounds and their uses as a medicament.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Autocatalytic oxidative addition of PhBr to Pd(PtBu 3)2 via Pd(PtBu3)2(H)(Br)

We report that oxidative addition of bromobenzene to Pd(PtBu3)2 occurs by an unusual autocatalytic mechanism. Studies on the effect of various additives showed that the degree of rate acceleration followed the trend: (PtBu3)Pd(Ph)(Br) ? (HPtBu3)Br < [(PtBu3)Pd(mu-Br)]2 < (PtBu3)2Pd(H)(Br). Studies on the reactions of Pd(PtBu3)2 in the presence of (PtBu3)2Pd(H)(Br) showed that the concentration of (PtBu3)2Pd(H)(Br) decreased only after the Pd(0) complex had been consumed. These data indicated that the catalyst in this process is (PtBu3)2Pd(H)(Br). Thermal decomposition of the three-coordinate oxidative addition product (PtBu3)Pd(Ar)(Br) during the reaction of Pd(PtBu3)2 and bromoarenes ultimately leads to formation of (PtBu3)2Pd(H)(Br). Parallel reactions of bromobenzene with (PtBu3)2Pd(H)(Br) and Pd(PtBu3)2 showed that the bromoarenes reacted considerably faster with the Pd(II) species than with the Pd(0) species. We therefore propose a catalytic cycle for oxidative addition in which PBut3·HBr reacts with the Pd(0) species to form (PtBu3)2Pd(H)(Br), and (PtBu3)2Pd(H)(Br) reacts with the bromoarene, possibly though the anionic species [HPtBu3+][(PtBu3)Pd(Br)-], to form [Pd(PtBu3)(Ar)(Br)]. Copyright I hope this article can help some friends in scientific research. I am very proud of our efforts over the past few months and hope to 53199-31-8, help many people in the next few years.SDS of cas: 53199-31-8

Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Computational study of PtBu3 as ligand in the palladium-catalysed amination of phenylbromide with morpholine

Computational study of the full catalytic cycle for the coupling of phenylbromide with morpholine (amination), catalysed by Pd(PtBu 3) complex, related to ligand design criteria.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A palladium-catalyzed methylenation of olefins using halomethylboronate reagents

Methylenation of electron-rich olefins is a highly challenging reaction, for which we have developed a new methodology exploiting Pd-catalysis and halomethylboronate reagents, the latter replacing diazomethane and zinc carbenoids as methylene donors. Optimization of the reaction for norbornene and extension to several other olefins are reported, with reasonable-to-excellent yields of cyclopropanes in combination with beta-H elimination products. Several mechanisms are plausible for this methylenation reaction.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Silacarboxylic acids as efficient carbon monoxide releasing molecules: Synthesis and application in palladium-catalyzed carbonylation reactions

Silacarboxylic acids have been demonstrated to be easy to handle, air-stable carbon monoxide precursors. Different silacarboxylic acids were synthesized from the corresponding chlorosilanes and carbon dioxide, and their decarbonylation, upon treatment with an array of activators, was evaluated. The release of CO from crystalline MePh2SiCO2H proved to be highly efficient, and it was successfully applied in a selection of palladium-catalyzed carbonylative couplings using near-stoichiometric quantities of carbon monoxide precursor. Finally, the synthesis of MePh2Si 13CO2H and its application in carbonyl labeling of two bioactive compounds was demonstrated.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method