Category: 1416819-91-4

Silva, Allan R.; Polo, Ellen C.; Martins, Nelson C.; Correia, Carlos Roque D. published the artcile< Enantioselective Oxy-Heck-Matsuda Arylations: Expeditious Synthesis of Dihydrobenzofuran Systems and Total Synthesis of the Neolignan (-)-Conocarpan>, Computed Properties of 1416819-91-4, the main research area is aryldiazonium salt styrenic olefin palladium Oxy Heck Matsuda arylation; dihydrobenzofuran stereoselective preparation.

This work discloses the first examples of an effective enantioselective oxy-Heck-Matsuda reaction using a variety of styrenic olefins to generate chiral dihydrobenzofurans I (R1 = 6-NO2, 5-NO2, 5-Me, etc.; R2 = 4-OMe, 4-OH, 2,4-OMe, etc.; R3 = Me, i-Pr). The reaction proceeds in moderate to good yields, with high trans diastereoselectivity (up to 20:1) in enantioselectivities up to 90:10 using the N,N-ligand pyrimidine-bisoxazoline (PyriBox). The oxy-Heck-Matsuda reactions were carried out under mild conditions and rather low catalyst loadings. The feasibility and practicality of the process is demonstrated by a concise total synthesis of the neolignan (-)-conocarpan. X-ray diffraction of an advanced brominated intermediate in the route to (-)-conocarpan has allowed the unequivocal assignment of the absolute stereochem. of the oxy-Heck-Matsuda aryldihydrobenzofuran products. A rationale for the mechanism operating in these enantioselective oxy-Heck-Matsuda reactions is also presented.

Advanced Synthesis & Catalysis published new progress about Benzofurans Role: SPN (Synthetic Preparation), PREP (Preparation) (Dihydro). 1416819-91-4 belongs to class pyridine-derivatives, and the molecular formula is C13H15F3N2O, Computed Properties of 1416819-91-4.

Referemce:
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem

Pezzetta, Cristofer; Bonifazi, Davide; Davidson, Robert W. M. published the artcile< Enantioselective Synthesis of N-Benzylic Heterocycles: A Nickel and Photoredox Dual Catalysis Approach>, Product Details of C13H15F3N2O, the main research area is benzylic heterocycle preparation enantioselective; heterocyclic carboxylic acid aryl bromide decarboxylative cross coupling; nickel photoredox dual catalysis.

Reported herein is a dual nickel- and photoredox-catalyzed modular approach for the preparation of enantioenriched N-benzylic heterocycles. α-Heterocyclic carboxylic acids, easily obtainable from common com. material, are reported as suitable substrates for a decarboxylative strategy in conjunction with a chiral pyridine-oxazoline (PyOx) ligand, providing quick access to enantioenriched drug-like products. The presence of a directing group on the heterocyclic moiety is shown to be beneficial, affording improved stereoselectivity in a number of cases.

Organic Letters published new progress about Aryl bromides Role: RCT (Reactant), RACT (Reactant or Reagent). 1416819-91-4 belongs to class pyridine-derivatives, and the molecular formula is C13H15F3N2O, Product Details of C13H15F3N2O.

Referemce:
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem

Zhang, Chun; Santiago, Celine B.; Kou, Lei; Sigman, Matthew S. published the artcile< Alkenyl Carbonyl Derivatives in Enantioselective Redox Relay Heck Reactions: Accessing α,β-Unsaturated Systems>, Formula: C13H15F3N2O, the main research area is arylboronic acid unsaturated carbonyl enantioselective regioselective arylation Heck; aryl unsaturated carbonyl stereoselective preparation.

A highly enantioselective and site-selective Pd-catalyzed arylation of alkenes linked to carbonyl derivatives to yield α,β-unsaturated systems is reported. The high site selectivity is attributed to both a solvent effect and the polarized nature of the carbonyl group, both of which have been analyzed through multidimensional anal. tools. The reaction can be performed in an iterative fashion allowing for a diastereoselective installation of two aryl groups along an alkyl chain.

Journal of the American Chemical Society published new progress about Arylation, stereoselective (regioselective). 1416819-91-4 belongs to class pyridine-derivatives, and the molecular formula is C13H15F3N2O, Formula: C13H15F3N2O.

Referemce:
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem

Xu, Liping; Hilton, Margaret J.; Zhang, Xinhao; Norrby, Per-Ola; Wu, Yun-Dong; Sigman, Matthew S.; Wiest, Olaf published the artcile< Mechanism, Reactivity, and Selectivity in Palladium-Catalyzed Redox-Relay Heck Arylations of Alkenyl Alcohols>, Recommanded Product: (S)-4-(tert-Butyl)-2-(5-(trifluoromethyl)pyridin-2-yl)-4,5-dihydrooxazole, the main research area is palladium catalyzed redox relay Heck arylation alkenyl alc mechanism.

The enantioselective Pd-catalyzed redox-relay Heck arylation of acyclic alkenyl alcs. allows access to various useful chiral building blocks from simple olefinic substrates. Mechanistically, after the initial migratory insertion, a succession of β-hydride elimination and migratory insertion steps yields a saturated carbonyl product instead of the more general Heck product, an unsaturated alc. Here, we investigate the reaction mechanism, including the relay function, yielding the final carbonyl group transformation. M06 calculations predict a ΔΔG# of 1 kcal/mol for the site selectivity and 2.5 kcal/mol for the enantioselectivity, in quant. agreement with exptl. results. The site selectivity is controlled by a remote electronic effect, where the developing polarization of the alkene in the migratory insertion transition state is stabilized by the C-O dipole of the alc. moiety. The enantioselectivity is controlled by steric repulsion between the oxazoline substituent and the alc.-bearing alkene substituent. The relay efficiency is due to an unusually smooth potential energy surface without high barriers, where the hydroxyalkyl-palladium species acts as a thermodn. sink, driving the reaction toward the carbonyl product. Computational predictions of the relative reactivity and selectivity of the double bond isomers are validated exptl.

Journal of the American Chemical Society published new progress about Alkenyl alcohols Role: PEP (Physical, Engineering or Chemical Process), PRP (Properties), RCT (Reactant), PROC (Process), RACT (Reactant or Reagent). 1416819-91-4 belongs to class pyridine-derivatives, and the molecular formula is C13H15F3N2O, Recommanded Product: (S)-4-(tert-Butyl)-2-(5-(trifluoromethyl)pyridin-2-yl)-4,5-dihydrooxazole.

Referemce:
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem

Chen, Guihua; Cao, Jian; Wang, Qian; Zhu, Jieping published the artcile< Desymmetrization of Prochiral Cyclopentenes Enabled by Enantioselective Palladium-Catalyzed Oxidative Heck Reaction>, Formula: C13H15F3N2O, the main research area is desymmetrization cyclopentene enantioselective oxidative Heck palladium catalyst; oxidative Heck arylboronic acid cyclopentene palladium catalyst diastereoselective enantioselective.

In the presence of a catalytic amount of Pd(TFA)2 and a chiral Pyox ligand under oxygen atm., oxidative Heck reaction between arylboronic acids and 4-substituted or 4,4-disubstituted cyclopent-1-enes afforded the chiral arylated products with concurrent creation of two stereocenters in good yields with excellent diastereo- and enantioselectivities.

Organic Letters published new progress about Arylboronic acids Role: RCT (Reactant), RACT (Reactant or Reagent). 1416819-91-4 belongs to class pyridine-derivatives, and the molecular formula is C13H15F3N2O, Formula: C13H15F3N2O.

Referemce:
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem

McCammant, Matthew S.; Sigman, Matthew S. published the artcile< Development and investigation of a site selective palladium-catalyzed 1,4-difunctionalization of isoprene using pyridine-oxazoline ligands>, Category: pyridine-derivatives, the main research area is pyridine oxazoline ligand preparation; polyene regioselective diastereoselective preparation; isoprene vinyl triflate vinylboronic acid palladium catalyst difunctionalization.

Palladium-catalyzed 1,4-difunctionalizations of isoprene that produce skipped polyenes were reported. Complex isomeric product mixtures were possible as a result of the difficult-to-control migratory insertion of isoprene into a Pd-alkenyl bond, but good site selectivity was achieved using easily accessible pyrox ligands. Mechanistic studies suggest that the control of insertion was the result of the unique electronic asymmetry and steric properties of the ligand.

Chemical Science published new progress about Addition reaction catalysts, stereoselective (regioselective). 1416819-91-4 belongs to class pyridine-derivatives, and the molecular formula is C13H15F3N2O, Category: pyridine-derivatives.

Referemce:
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem

Dang, Yanfeng; Qu, Shuanglin; Wang, Zhi-Xiang; Wang, Xiaotai published the artcile< A Computational Mechanistic Study of an Unprecedented Heck-Type Relay Reaction: Insight into the Origins of Regio- and Enantioselectivities>, Related Products of 1416819-91-4, the main research area is Heck type relay reaction mechanism regioselectivity enantioselectivity.

D. functional theory (DFT) calculations (B3LYP and M06) have been utilized to study a newly reported Heck-type reaction that uses an allylic or alkenyl alc. as substrate and palladium as catalyst in the form of a chelate with a chiral pyridine oxazoline (PyrOx) ligand. The reaction not only controls the regio- and enantioselectivities of arylation of the C=C bond, but also forms the carbonyl functionality up to four bonds away from the aryl substituent via tandem C=C bond migration and enol-to-keto conversion. Computations performed on representative reaction systems allow us to propose a detailed mechanism with several key steps. Initial oxidation of palladium(0) by aryldiazonium generates active arylpalladium(II) species that bind the C=C bond of an allylic or alkenyl alc. The activated C=C bond inserts into the palladium-aryl moiety to attain aryl substitution and a chiral carbon center, and the resulting complex undergoes β-hydride elimination to give a new C=C bond that can repeat the insertion/elimination process to move down the carbon chain to form an enol that tautomerizes to a highly stable carbonyl final product. The calculations reveal that the C=C bond migratory insertion step determines both the regioselectivity and the enantioselectivity of arylation, with the former arising mainly from the electronic effect of the hydroxyl group on the charge distribution over the C=C bond and the latter originating from a combination of steric repulsion, trans influence, and C-H/π dispersion interactions.

Journal of the American Chemical Society published new progress about Alkenyl alcohols Role: PEP (Physical, Engineering or Chemical Process), PRP (Properties), RCT (Reactant), PROC (Process), RACT (Reactant or Reagent). 1416819-91-4 belongs to class pyridine-derivatives, and the molecular formula is C13H15F3N2O, Related Products of 1416819-91-4.

Referemce:
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem

Nakamura, Hugh; Yasui, Kosuke; Kanda, Yuzuru; Baran, Phil S. published the artcile< 11-Step Total Synthesis of Teleocidins B-1-B-4>, Category: pyridine-derivatives, the main research area is teleocidin B synthesis.

A unified and modular approach to the teleocidin B family of natural products is presented that proceeds in 11 steps and features an array of interesting strategies and methods. Indolactam V, the known biosynthetic precursor to this family, was accessed through electrochem. amination, Cu-mediated aziridine opening, and a remarkable base-induced macrolactamization. Guided by a desire to minimize concession steps, the tactical combination of C-H borylation and a Sigman-Heck transform enabled the convergent, stereocontrolled synthesis of the teleocidins.

Journal of the American Chemical Society published new progress about Amination (electrochem.). 1416819-91-4 belongs to class pyridine-derivatives, and the molecular formula is C13H15F3N2O, Category: pyridine-derivatives.

Referemce:
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem

Patel, Harshkumar H.; Sigman, Matthew S. published the artcile< Palladium-Catalyzed Enantioselective Heck Alkenylation of Acyclic Alkenols Using a Redox-Relay Strategy>, Product Details of C13H15F3N2O, the main research area is alkenyl triflate alkenol acyclic palladium Heck alkenylation catalyst; aldehyde acyclic stereoselective preparation.

We report a highly enantioselective intermol. Heck reaction of alkenyl triflates and acyclic primary or racemic secondary alkenols. The mild reaction conditions permit installation of a wide range of alkenyl groups at positions β, γ, or δ to a carbonyl group in high enantioselectivity. The success of this reaction is attributed to the use of electron-withdrawing alkenyl triflates, which offer selective β-hydride elimination followed by migration of the catalyst through the alkyl chain to give the alkenylated carbonyl products. The synthetic utility of the process is demonstrated by a two-step modification of a reaction product to yield a tricyclic core structure, present in various natural products.

Journal of the American Chemical Society published new progress about Aliphatic aldehydes Role: SPN (Synthetic Preparation), PREP (Preparation). 1416819-91-4 belongs to class pyridine-derivatives, and the molecular formula is C13H15F3N2O, Product Details of C13H15F3N2O.

Referemce:
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem

Lamb, Claire J. C.; Vilela, Filipe; Lee, Ai-Lan published the artcile< Pd(II)-Catalyzed Enantioselective Desymmetrization of Polycyclic Cyclohexenediones: Conjugate Addition versus Oxidative Heck>, Product Details of C13H15F3N2O, the main research area is polycyclic cyclohexenedione arylboronic acid stereoselective palladium desymmetrization Heck reaction.

Pd(II)-catalyzed desymmetrization of polycyclic cyclohexenediones has been achieved with high enantio- and diastereoselectivities. Up to five contiguous stereocenters are desymmetrized, while simultaneously, an addnl. stereocenter is created by the enantioselective conjugate addition Surprisingly, the conjugate addition products dominate even under typical oxidative Heck conditions, and these observations may provide some insight into the competition between the two related reactions.

Organic Letters published new progress about Arylboronic acids Role: RCT (Reactant), RACT (Reactant or Reagent). 1416819-91-4 belongs to class pyridine-derivatives, and the molecular formula is C13H15F3N2O, Product Details of C13H15F3N2O.

Referemce:
Pyridine – Wikipedia,
Pyridine | C5H5N – PubChem