characterizing-lewis-pairs-using-titration-coupled-with-situ-infrared

Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy

Lewis acid-activation of carbonyl-containing substrates is a fundamental basis for facilitating transformations in organic chemistry. Historically, ...

Loyola University Chicago

Iron(III)-catalyzed carbonyl-olefin ring-closing metathesis represents a new approach toward the assembly of molecules traditionally generated by olefin-olefin metathesis or olefination. Herein, we report detailed synthetic, spectroscopic, kinetic, and computational studies to determine the mechanistic features imparted by iron(III), substrate, and temperature to the catalytic cycle. These data are consistent with an iron(III)-mediated asynchronous, concerted [2+2]-cycloaddition to form an intermediate oxetane as the turnover-limiting step. Fragmentation of the oxetane via Lewis acid-activation results in the formation of five- and six-membered unsaturated carbocycles.

Mechanistic Investigations of the Iron(III)-Catalyzed Carbonyl-Olefin Metathesis Reaction.

Iron(III)-catalyzed carbonyl-olefin ring-closing metathesis employs reactivity not typically observed in Lewis acid-catalyzed reactions. In converting a ketone with a pendant olefin into a cycloalkene and a simple carbonyl byproduct, the reaction requires the Lewis acid catalyst to differentiate between the carbonyl of the substrate and that of the byproduct. It is necessary to determine how this solution interaction imparts the desired reactivity to best employ this method. Herein, we report detailed kinetic, spectroscopic, and colligative measurements applied toward the identification of the solution structures of the active Fe(III) and Ga(III) carbonyl-olefin metathesis catalysts. These data are consistent with formation of Lewis acid-carbonyl pairs for both metal systems under stoichiometric conditions. However, they diverge in the presence of higher equivalents of carbonyl, with Fe(III) forming highly ligated complexes, and no observed change for Ga(III). These findings are consistent with the resting state identity of the Fe(III) metathesis catalyst changing over the course of the reaction.

Catalyst Behavior in Metal-Catalyzed Carbonyl-Olefin Metathesis.

Lewis acid-activation of carbonyl-containing substrates is broadly utilized in organic synthesis. In order to facilitate the development of novel reaction pathways and understand existing methods, it is necessary to determine the solution interactions between Lewis acids and Lewis bases. Herein, we report the application of in situ infrared spectroscopy and solution conductivity toward the identification of the solution structures formed when a range of carbonyl compounds are combined with catalytically active metal halide Lewis acids under synthetically relevant conditions. These data are consistent with formation of Lewis acid-dependent complexes, where metals of low relative Lewis acidity display no ground state interaction with carbonyls. Conversely, we observed the formation of polyligated complexes when stronger Lewis acids (SnCl, TiCl, ZrCl, FeCl, and AlCl) were treated with ketones, aldehydes, and esters. This collection of observations is intended to assist the synthetic chemist in the design of new catalysts and the development of novel methods.

Article	Year
Mechanistic Investigations of the Iron(III)-Catalyzed Carbonyl-Olefin Metathesis Reaction. Journal of the American Chemical Society\| PubMed ID: 28753008	2017
Catalyst Behavior in Metal-Catalyzed Carbonyl-Olefin Metathesis. Journal of the American Chemical Society\| PubMed ID: 31276383	2019
Investigation of Lewis Acid-Carbonyl Solution Interactions via Infrared-Monitored Titration. The Journal of organic chemistry\| PubMed ID: 31830419	2020

James J. Devery

Biography

JoVE Journal Publications

Other Publications