Fast reactions at planar four-co-ordinate complexes. Part 5. The solvent effect on the leaving group in the reactions of neutral and cationic palladium(II) complexes

Responding to a stimulus that had to be ignored previously is usually slowed-down (negative priming effect). This study investigates the reaction time and ERP effects of the negative priming phenomenon in the auditory domain. Thirty participants had to categorize sounds as musical instruments or animal voices. Reaction times were slowed-down in the negative priming condition relative to two control conditions. This effect was stronger for slow reactions (above intraindividual median) than for fast reactions (below intraindividual median). ERP analysis revealed a parietally located negativity of the negative priming condition compared to the control conditions between 550-730 ms poststimulus. This replicates the findings of Mayr, Niedeggen, Buchner, and Pietrowsky (2003) . The ERP correlate was more pronounced for slow trials (above intraindividual median) than for fast trials (below intraindividual median). The dependency of the negative priming effect size on the reaction time level found in the reaction time analysis as well as in the ERP analysis is consistent with both the inhibition as well as the episodic retrieval account of negative priming. A methodological artifact explanation of this effect-size dependency is discussed and discarded.

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Solvent Effect on Optical Rotation I Optical Rotation ofl-Santonin

Zeitschrift für Physikalische Chemie ◽

10.1524/zpch.1960.25.1_2.056 ◽

1960 ◽

Vol 25 (1_2) ◽

pp. 56-68 ◽

Cited By ~ 2

Author(s):

A. J. Mukhedkar

Keyword(s):

Solvent Effect ◽

Optical Rotation

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Kinetic Solvent Effects in Organic Reactions

10.26434/chemrxiv.5370778.v1 ◽

2017 ◽

Author(s):

Belinda Slakman ◽

Richard West

Keyword(s):

Solvent Effect ◽

Reaction Kinetics ◽

Computational Methods ◽

High Throughput ◽

Kinetic Modeling ◽

Solvent Effects ◽

Reaction Rates ◽

Prior Work ◽

Solvent Phase ◽

High Throughput Manner

<div> <div> <div> <p>This article reviews prior work studying reaction kinetics in solution, with the goal of using this information to improve detailed kinetic modeling in the solvent phase. Both experimental and computational methods for calculating reaction rates in liquids are reviewed. Previous studies, which used such methods to determine solvent effects, are then analyzed based on reaction family. Many of these studies correlate kinetic solvent effect with one or more solvent parameters or properties of reacting species, but it is not always possible, and investigations are usually done on too few reactions and solvents to truly generalize. From these studies, we present suggestions on how best to use data to generalize solvent effects for many different reaction types in a high throughput manner. </p> </div> </div> </div>

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General Cyclopropane Assembly via Enantioselective Redox-Active Carbene Transfer to Aliphatic Olefins

10.26434/chemrxiv.7436795 ◽

2018 ◽

Author(s):

Marc Montesinos-Magraner ◽

Matteo Costantini ◽

Rodrigo Ramirez-Contreras ◽

Michael E. Muratore ◽

Magnus J. Johansson ◽

...

Keyword(s):

Total Synthesis ◽

Asymmetric Synthesis ◽

Chemical Space ◽

Synthetic Approach ◽

Asymmetric Cyclopropanation ◽

Redox Active ◽

Wide Range ◽

Leaving Group ◽

Stereoelectronic Properties ◽

Carbene Transfer

Asymmetric cyclopropane synthesis currently requires bespoke strategies, methods, substrates and reagents, even when targeting similar compounds. This limits the speed and chemical space available for discovery campaigns. Here we introduce a practical and versatile diazocompound, and we demonstrate its performance in the first unified asymmetric synthesis of functionalized cyclopropanes. We found that the redox-active leaving group in this reagent enhances the reactivity and selectivity of geminal carbene transfer. This effect enabled the asymmetric cyclopropanation of a wide range of olefins including unactivated aliphatic alkenes, enabling the 3-step total synthesis of (–)-dictyopterene A. This unified synthetic approach delivers high enantioselectivities that are independent of the stereoelectronic properties of the functional groups transferred. Our results demonstrate that orthogonally-differentiated diazocompounds are viable and advantageous equivalents of single-carbon chirons<i>.</i>

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