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Catalytic Z -selective cross-metathesis in complex molecule synthesis: A convergent stereoselective route to disorazole C1

A convergent diastereo- and enantioselective total synthesis of anticancer and antifungal macrocyclic natural product disorazole C1 is reported. The central feature of the successful route is the application of catalytic Z-selective cross-metathesis (CM). Specifically, we illustrate that catalyst-controlled stereoselective CM can be performed to afford structurally complex Z-alkenyl-B(pin) as well as Z-alkenyl iodide compounds reliably, efficiently, and with high selectivity (pin = pinacolato). The resulting intermediates are then joined in a single-step operation through catalytic inter- and intramolecular cross-coupling to furnish the desired 30-membered ring macrocycle containing the critical (Z,Z,E)-triene moieties.

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

Discovery of Bis(tri-o-tolylphosphine)palladium(0)

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Key factors for high diastereo- And enantioselectivity of umpolung cyclizations of aldehyde-containing allylpalladium intermediates

Two palladium/chiral diphosphine-catalyzed umpolung cyc-lizations of aldehyde-containing allylic acetates and allenes with arylboronic acid are fully investigated to establish key factors in their high stereoselectivities. Both cyclization reactions afford cis-disubstituted pyrrolidine and tetrahydrofuran. These occur in high diastereo- and enantioselectivities through a common cationic (Z)-eta1-allylpalladium, toward which a ring strain generated in the cyclization step leading to trans-isomers biases the equilibrium through eta3-eta1-eta3-complex in the former cyclization. Varied diastereoselectivities were observed in the formation of five-membered carbocycles and six-membered heterocycles. These reflect release of a ring strain generated in the cyclization step leading to trans-isomers and a different distribution of the (Z)- and the (E)-eta1-allylpalladium intermediates generated by the oxidative addition of allylic acetates to Pd(0) or carbopalladation of allenes, respectively. A steri-cally demanding substituent at the center of the allyl moiety is necessary for high diastereo- and enantioselectivity. The enantioselectivity of the former cyclization was lowered by the presence of organometallic reductants or reagents, possibly causing the formation of neutral eta1-allylpalladium species. We used a chiral allylic acetate containing (E)-deuterium-labeled alkene to demonstrate that the electrophilic attack of the aldehyde to the allyl ligand occurred on the side where the palladium existed, consistent with the Zimmerman-Traxler transition state.

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

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Palladium-catalyzed carboiodination of alkenes: Carbon-carbon bond formation with retention of reactive functionality

We report a palladium-catalyzed carbon-carbon bond-forming reaction between aryl iodides and alkenes. In contrast to traditional cross-coupling reactions, two new bonds are formed, and all of the atoms in the starting materials are incorporated into the product. The use of a palladium catalyst with bulky phosphine ligands is found to be crucial for reactivity.

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

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Pd-Catalyzed Decarbonylative Cross-Couplings of Aroyl Chlorides

This report describes a method for Pd-catalyzed decarbonylative cross-coupling that enables the conversion of carboxylic acid derivatives to biaryls, aryl amines, aryl ethers, aryl sulfides, aryl boronate esters, and trifluoromethylated arenes. The success of this transformation leverages the Pd0/Brettphos-catalyzed decarbonylative chlorination of aroyl chlorides, which can then participate in diverse cross-coupling reactions in situ using the same Pd catalyst.

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

New explortion of Bis(tri-o-tolylphosphine)palladium(0)

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A PROCESS FOR PREPARING 2-HYDROXY-3- [5- (MORPHOLIN-4-YLMETHYL)PYRIDIN-2-YL] LH-INDOLE-5-CARBONITRILE AS A FREE BASE OR SALTS THEREOF

The present invention relates to a new process for the manufacture of the compound 2-hydroxy-3-[5-(mopholin-4-ylmethyl)pyridin-2-yl]lH’-indole-5-carbonitrile as a free base and pharmaceutically acceptable salts thereof, particularly the 2-hydroxy-3-[5- (morpholm-4-ylmethyl)pyridin-2-yl]lH-indole-5-carbonitrile citrate, to the use of said compounds for the manufacturing of a medicament for the treatment of cognitive disorders, Alzheimer disease, dementias, chronic and acute neurodegenerative diseases, bipolar disorders, schizophrenia, diabetes, hair loss etc. and to new intermediates as well as a robust condition for catalytic cyanation for the preparation of 2-hydroxy-3-[5- (mopholin-4-yhnethyl)pyridin-2-yl]lH-indole-5-carbonitrile as a free base and pharmaceutically acceptable salts thereof, and to a new intermediate prepared in said process suitable for large scale manufacturing of said compounds.The invention also relates to a new use in cyanation reaction of palladium catalysts

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

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Synthetic Route of 69861-71-8, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.69861-71-8, Name is Bis(tri-o-tolylphosphine)palladium(0), molecular formula is C42H42P2Pd. In a article£¬once mentioned of 69861-71-8

Synthesis of fluoroalkyl palladium and nickel complexes via decarbonylation of acylmetal species

The synthesis and characterization of a series of fluoroalkyl palladium(II) and nickel(II) complexes via decarbonylation of the corresponding acylmetal species is reported. At palladium(II), labile supporting ligands such as tri-o-tolylphosphine are required to achieve decarbonylation within 30 min at 85 C. In contrast, decarbonylation at (PPh3)2Ni(C(O) RF)(OCORF) (RF = fluoroalkyl) complexes proceeds rapidly at or below room temperature.

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

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Asymmetric palladium-catalyzed umpolung cyclization of allylic acetate-aldehyde using formate as a reductant

Palladium/chiral diphosphine-catalyzed umpolung cyclization of allylic acetate-aldehyde using formate as a terminal reductant affords cis-disubstituted pyrrolidine, tetrahydrofuran, and spiro carbocycle in high enantioselectivity. The formate does not cause allylpalladium reduction under the catalysis. The highly stereoselective cyclization would proceed through a cationic eta1-allylpalladium ligated by diphosphine.

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

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1,6-Diene complexes of palladium(0) and platinum(0): Highly reactive sources for the naked metals and [L-M0] fragments

The complexes (cod)MCl2 (M = Pd, Pt; cod = cis,cis-1,5-cyclooctadiene) react with Li2(cot) (cot = cyclooctatetraene) in a 1,6-diene/diethyl ether mixture (1,6-diene = hepta-1,6-diene, diallyl ether, dvds (1,3-divinyl- 1,1,3,3-tetramethyldisiloxane)) to afford the isolated homoleptic dinuclear Pd0 and Pt0 compounds Pd2(C7H12)3 (1), Pd2(C6H10O)3¡¤C6H10O (2′; 2: Pd2(C6H10O)3), Pd2(dvds)3 (3), and Pt2(C7H12)3 (4). When 1-4 are treated with additional 1,6-diene the equally homoleptic but mononuclear derivatives of type M(1,6-diene)2 (5-8) and with ethene the mixed alkene complexes (C2H4)M(1,6-diene) (9-12) are obtained in solution. Complexes 1-12 react with donor ligands such as phosphanes, phosphites, or (t)BuNC to give isolated complexes of types L-M(1,6-diene) (13-41), which have also been prepared by other routes. In all complexes the metal centers are TP-3 coordinated: complexes 1-4 contain chelating and bridging 1,6-diene ligands, whereas the other complexes contain a chelating 1,6-diene ligand and an eta2-alkene (5-12) or eta1-donor ligand (13-41). Of the studied 1,6-diene complexes the hepta-1,6-diene derivatives are most reactive, while the diallyl ether complexes are often more convenient to handle. The readily isolable dinuclear hepta-1,6-diene and diallyl ether complexes 1, 2′, and 4, and their mononuclear pure olefin derivatives are among the most reactive sources for naked Pd0 and Pt0. The corresponding L-M(1,6-diene) complexes are equally reactive precursor compounds for the generation of [L-M0] fragments in solution, which for M =Pd are available otherwise only with difficulty. The results are significant for the operation of naked Pd0 and L-Pd0 catalysts in homogeneous catalysis.

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

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Palladium-Catalyzed Carbon Isotope Exchange on Aliphatic and Benzoic Acid Chlorides

An operationally simple protocol for a palladium-catalyzed 13CO and 14CO exchange with activated aliphatic and benzoic carbonyls is presented. Several 13C and 14C building blocks, natural product derivatives, and pharmaceuticals have been prepared to showcase the method for late-stage carbon isotope incorporation and its functional group compatibility.

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

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Application of palladacycles in Heck type reactions

In the last 3 years, there have been tremendous developments in palladium catalytic systems for Heck type reactions. One of the successful approaches towards activation of less reactive substrates like aryl chlorides involves the use of palladacycles 1, 2 and 3 as catalyst precursors. This article describes the principles of these systems with an emphasis on our own work and features the ongoing literature discussion about possible mechanisms involving Pd(0)/Pd(II) or Pd(II)/Pd(IV) catalytic cycles for this class of catalyst.

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