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Regiodivergent Synthesis of Pyrazolines with a Quaternary Carbon Center via Cycloaddition of Diazoesters to N-Purine-Substituted Allenes

Diversity-oriented synthesis of pyrazoline derivatives that contain a quaternary carbon center has been achieved via the 1,3-dipolar cycloaddition between N-purine-substituted allenes and alpha-alkyl/aryl diazoesters. Using Pd2(dba)3 as a catalyst, only 1-pyrazoline derivatives are produced in a regioselective manner. When DPPB is used as a catalyst, diverse 1-pyrazolines and 2-pyrazolines are obtained in moderate to good total yields.

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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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Synthesis of Pyrazolo[5,1-a]isoquinolines and 8-Methylenepyrazolo[5,1-a]isoindoles via Regioselective C-C Coupling and Alkyne Hydroamination

An efficient and convenient synthesis of pyrazolo[5,1-a]isoquinolines has been achieved via palladium-catalyzed Sonogashira coupling of terminal alkynes with 5-(2-bromophenyl)-1H-pyrazoles, in situ formed from the condensation of 1-(2-bromophenyl)buta-2,3-dien-1-ones with hydrazine hydrate, followed by 6-endo intramolecular alkyne hydroamination. More interestingly, 8-methylenepyrazolo[5,1-a]isoindoles, the regioisomer of pyrazolo[5,1-a]isoquinolines, could also be selectively synthesized from the same starting materials through an initial intermolecular hydroamination of terminal alkynes with 5-(2-bromophenyl)-1H-pyrazoles followed by a palladium-catalyzed 5-exo intramolecular Heck coupling reaction.

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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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METHOD FOR DEUTERATION OR TRITIATION OF HETEROCYCLIC RING

The present invention relates to a method for deuteration of a heterocyclic ring, which comprises subjecting a compound having a heterocyclic ring to sealed refluxing state in a deuterated solvent in the presence of an activated catalyst selected form a palladium catalyst, a platinum catalyst, a rhodium catalyst, a ruthenium catalyst, a nickel catalyst and a cobalt catalyst. In accordance with a method of the present invention, a hydrogen atom belonging to a heterocyclic ring of a compound having a heterocyclic ring can be very efficiently deuterated because temperature of deuteration reaction can be maintained at higher than boiling point of the solvent.Further, a method for deuteration of the present invention can be applied widely to deuteration of various compounds having a heterocyclic ring which are liable to decomposition under supercritical conditions or acidic conditions, leading to industrial and efficient deuteration of a compound having a heterocyclic ring.

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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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Rapid access to diverse alpha-carbolines through sequential transition metal catalyzed amination and direct C-H arylation

An efficient sequence of Pd catalyzed amination and direct C-H arylation for a synthesis of pharmacologically important alpha-carbolines is described. The outstanding feature in the synthetic sequence is that a combination of DBU and 2-(dicyclohexylphosphino)biphenyl (DCHPB) plays a critical role to not only enhance the reactivity but also suppress hydrodehalogenation in the direct C-H arylation step. The reaction protocol provides alpha-carbolines with various substituents including base-sensitive ester and ketone moieties in moderate to excellent yields. Moreover, combination with Cu catalyzed amination further enhanced the versatility of the alpha-carboline synthesis.

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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 Enantioselective Decarboxylative Allylic Alkylation of Protected Benzoin-Derived Enol Carbonates

The enantioselective palladium-catalyzed decarboxylative allylic alkylation of fully substituted alpha-hydroxy acyclic enol carbonates providing tetrasubstituted benzoin derivatives is reported. Investigation into the transformation revealed that preparation of the starting material as a single enolate isomer is crucial for optimal enantioselectivity. The obtained alkylation products contain multiple reactive sites that can be utilized toward the synthesis of stereochemically rich derivatives. (Figure presented.).

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

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Monodentate Phosphorus Ligand-Enabled General Palladium-Catalyzed Allylic C-H Alkylation of Terminal Alkenes

Monodentate phosphorus ligands have been found to enable the palladium-catalyzed allylic C-H alkylation reaction of terminal alkenes with a wide variety of carbon nucleophiles. Moreover, an asymmetric allylic C-H alkylation of terminal alkenes with pyrazol-5-ones has been established in the presence of chiral phosphoramidite ligand and chiral phosphoric acid as co-catalyst. Mechanistic studies suggest that a ternary Pd(0) complex, coordinated with a monodentate phosphorus ligand, benzoquinone, and alkene, is most likely to be an active species.

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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(PPh3)4-catalyzed direct ortho-fluorination of 2-arylbenzothiazoles with an electrophilic fluoride N-fluorobenzenesulfonimide (NFSI)

An efficient protocol was developed for regio-selective Pd-catalyzed direct ortho-fluorination of 2-arylbenzo[d]thiazoles using N-fluorobenzenesulfonimide (NFSI) as the F+ source, and l-proline as the crucial promoter. The present method offered a practical route to synthesize valuable fluorinated products, which are of potential importance in the pharmaceutical and agrochemical industries.

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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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A straightforward entry to chiral carbocyclic nucleoside analogues via the enantioselective [3+2] cycloaddition of alpha-nucleobase substituted acrylates

A straightforward entry to chiral carbocyclic nucleoside analogues has been realized via the enantioselective [3+2] cycloaddition of alpha-nucleobase substituted acrylates to vinyl cyclopropanes for the first time. With Pd2(dba)3-L5 as the catalyst, carbocyclic purine, uracil, and thymine nucleoside analogues with quaternary stereocenters were obtained in excellent yields (up to 99% yield) and good enantioselectivities (up to 92% ee).

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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 Enantioselective Alkenylation of Enelactams Using a Relay Heck Strategy

In this report, a palladium-catalyzed redox-relay Heck process to access optically active alkenylated alpha,beta-unsaturated lactams is described. Under mild reaction conditions, electron-deficient alkenyl triflates and electron-rich alkenyl iodonium salts undergo enantioselective and site-selective coupling with enelactams to deliver the products in high yields and excellent enantioselectivities. Furthermore, the products allow facile access to natural products such as (+)-calvine and (+)-2-epicalvine in addition to the bioactive molecule aza-goniothalamin.

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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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Redox-modulated near-infrared electrochromism, electroluminochromism, and aggregation-induced fluorescence change in an indolo[3,2-b]carbazole-bridged diamine system

A new indolo[3,2-b]carbazole-based compound (1) has been developed by linking two redox-active diphenylamine moieties to the rigid pi-conjugated indolo[3,2-b]carbazole core. Its first two completely reversible oxidation steps are mainly related to the two terminal amine centers, and a moderate electron coupling between these amine centers has been determined. The associated oxidized species 1+and 12+both exhibited strong NIR absorptions, and a completely reversible conversion among three different colors (light-yellow, red, and blue, corresponding to neutral, monocationic and dicationic states, respectively) could be realized. In addition, reversible switching between turn-off and turn-on of its fluorescence could be accomplished by electrochemical oxidation and reduction, respectively. Compound 1 also exhibited obvious fluorescence color changes during its aggregate-forming process, and its solid showed bright-yellow fluorescence with a high emission quantum yield of 30%.

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