ChemInform Abstract: Diastereoselective Access to Polyoxygenated Polycyclic Spirolactones Through a Rhodium-Catalyzed [3 + 2] Cycloaddition Reaction: Experimental and Theoretical Studies.

ChemInform ◽  
2013 ◽  
Vol 44 (27) ◽  
pp. no-no
Author(s):  
Fabien Rodier ◽  
Michel Rajzmann ◽  
Jean-Luc Parrain ◽  
Gaelle Chouraqui ◽  
Laurent Commeiras
Keyword(s):  
Cycloaddition Reaction ◽  
Theoretical Studies ◽  
Experimental And Theoretical Studies

scholarly journals Combined experimental and theoretical studies of regio- and stereoselectivity in reactions of β-isoxazolyl- and β-imidazolyl enamines with nitrile oxides

2016 ◽  
Vol 12 ◽  
pp. 2390-2401 ◽  
Author(s):  
Ilya V Efimov ◽  
Marsel Z Shafikov ◽  
Nikolai A Beliaev ◽  
Natalia N Volkova ◽  
Tetyana V Beryozkina ◽  
...  
Keyword(s):  
Room Temperature ◽  
Cycloaddition Reaction ◽  
Theoretical Studies ◽  
Dispersion Correction ◽  
Dioxane Solution ◽  
Theoretical Methods ◽  
Effective Catalyst ◽  
Nitrile Oxides ◽  
Catalyst Free ◽  
Experimental And Theoretical Studies

Reactions of β-azolyl enamines and nitrile oxides were studied by both experimental and theoretical methods. (E)-β-(4-Nitroimidazol-5-yl), (5-nitroimidazol-4-yl) and isoxazol-5-yl enamines smoothly react regioselectively at room temperature in dioxane solution with aryl, pyridyl, and cyclohexylhydroxamoyl chlorides without a catalyst or a base to form 4-azolylisoxazoles as the only products in good yields. The intermediate 4,5-dihydroisoxazolines were isolated as trans isomers during the reaction of (E)-β-imidazol-4-yl enamines with aryl and cyclohexylhydroxamoyl chlorides. Stepwise and concerted pathways for the reaction of β-azolyl enamines with hydroxamoyl chlorides were considered and studied at the B3LYP/Def2-TZVP level of theory combined with D3BJ dispersion correction. The reactions of benzonitrile oxide with both E- and Z-imidazolyl enamines have been shown to proceed stereoselectively to form trans- and cis-isoxazolines, respectively. The preference of E-isomers over Z-isomers, driven by the higher stability of the former, apparently controls the stereoselectivity of the investigated cycloaddition reaction with benzonitrilе oxide. Based on the reactivity of azolyl enamines towards hydroxamoyl chlorides, a novel, effective catalyst-free method was elaborated to prepare 4-azolyl-5-substituted isoxazoles that are otherwise difficult to obtain.

Regioselectivity and Reactivity of Intramolecular [2+2] Cycloaddition Reactions of Acyl Ketenes: Experimental and Theoretical Studies

Synlett ◽  
2018 ◽  
Vol 29 (14) ◽  
pp. 1836-1841 ◽  
Author(s):  
Mahboobeh Zahedifar ◽  
Hassan Sheibani ◽  
Vahid Saheb
Keyword(s):  
Ring Opening ◽  
Density Functional ◽  
Cycloaddition Reaction ◽  
Density Functional Theory Calculations ◽  
Theoretical Studies ◽  
Aryl Group ◽  
Functional Theory ◽  
Electron Withdrawing Group ◽  
Experimental And Theoretical Studies ◽  
Mechanism Of The Reaction

The regioselectivity of the intramolecular [2+2] cycloaddition reaction of acyl ketenes formed from metastable mesoionic 1,3-oxazinium-4-olates was investigated by experimental and theoretical methods. The ring opening of the mesoionic N-allyl-2-(2-arylvinyl)-1,3-oxazinium-4-olates led to the formation of unstable acyl ketenes. ­Although there are four possible paths for an intramolecular [2+2] cyclo­addition reaction involving the two double bonds (vinyl and allyl), only the intramolecular [2+2] criss-cross cycloaddition reaction through the vinyl double bond occurred to give 3-allyl-3-azabicyclo[3.1.1]heptane-2,4,6-trione derivatives. These products were not formed when a strongly electron-withdrawing group was present on the aryl group of acrylamides or benzamides. To understand the mechanism of the reaction, density functional theory calculations at the M06-2X/6-31+G(d) level were performed. These revealed that the formation of some preliminary intermediates plays a significant role in the formation of mesoionic 1,3-oxazinium-4-olates.

The Stabilizing Effect of Pre-Equilibria: A Trifluoromethyl Complex as CF2 Reservoir in Catalytic Olefin Difluorocarbenation

2020 ◽  
Author(s):  
Thomas Louis-Goff ◽  
Huu Vinh Trinh ◽  
Eileen Chen ◽  
Arnold L. Rheingold ◽  
Christian Ehm ◽  
...  
Keyword(s):  
High Selectivity ◽  
Side Reactions ◽  
Theoretical Studies ◽  
Attractive Feature ◽  
Catalyst Recovery ◽  
Wide Range ◽  
Stabilizing Effect ◽  
Experimental And Theoretical Studies

A new, efficient, catalytic difluorocarbenation of olefins to give 1,1-difluorocyclopropanes is presented. The catalyst, an organobismuth complex, uses TMSCF<sub>3</sub> as a stoichiometric difluorocarbene source. We demonstrate both the viability and robustness of this reaction over a wide range of alkenes and alkynes, including electron-poor alkenes, to generate the corresponding 1,1-difluorocyclopropanes and 1,1-difluorocyclopropenes. Ease of catalyst recovery from the reaction mixture is another attractive feature of this method. In depth experimental and theoretical studies showed that the key difluorocarbene-generating step proceeds through a bismuth non-redox synchronous mechanism generating a highly reactive free CF<sub>2</sub> in an endergonic pre-equilibrium. It is the reversibility when generating the difluorocarbene that accounts for the high selectivity, while minimizing CF<sub>2</sub>-recombination side-reactions.

Strong coupling: resonant effects

2017 ◽  
Author(s):  
Alexey V. Kavokin ◽  
Jeremy J. Baumberg ◽  
Guillaume Malpuech ◽  
Fabrice P. Laussy
Keyword(s):  
Strong Coupling ◽  
Experimental Studies ◽  
Strong Coupling Regime ◽  
Theoretical Studies ◽  
Stimulated Scattering ◽  
Quantum Theories ◽  
Pump Probe ◽  
Exciton Polaritons ◽  
Linear Optical Properties ◽  
Experimental And Theoretical Studies

This chapter presents experimental studies performed on planar semiconductor microcavities in the strong-coupling regime. The first section reviews linear experiments performed in the 1990s that evidence the linear optical properties of cavity exciton-polaritons. The chapter is then focused on experimental and theoretical studies of resonantly excited microcavity emission. We mainly describe experimental configuations in which stimulated scattering was observed due to formation of a dynamical condensate of polaritons. Pump-probe and cw experiments are described in addition. Dressing of the polariton dispersion and bistability of the polariton system due to inter-condensate interactions are discussed. The semiclassical and the quantum theories of these effects are presented and their results analysed. The potential for realization of devices is also discussed.

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