Publications by authors named "Timothy P McFadden"

Microbial electrosynthesis (MES) is a rapidly growing technology at the forefront of sustainable chemistry, leveraging the ability of microorganisms to catalyze electrochemical reactions to synthesize valuable compounds from renewable energy sources. The reduction of CO is a major target application for MES, but research in this area has been stifled, especially with the use of direct electron transfer (DET)-based microbial systems. The major fundamental hurdle that needs to be overcome is the low efficiency of CO reduction largely attributed to minimal microbial access to CO owing to its low solubility in the electrolyte.

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Grubbs 3rd-generation (G3) pre-catalyst-initiated ring-opening metathesis polymerization (ROMP) remains an indispensable tool in the polymer chemist's toolbox. Tricyclononenes (TCN) and tricyclononadienes (TCND) represent under-explored classes of monomers for ROMP that have the potential to both advance fundamental knowledge (, structure-polymerization kinetics relationships) and serve as practical tools for the polymer chemist (, post-polymerization functionalization). In this work, a library of TCN and TCND imides, monoesters, and diesters, along with their -norbornene counterparts, were synthesized to compare their behaviors in G3-initiated ROMP.

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The rate of frontal ring-opening metathesis polymerization (FROMP) using the Grubbs generation II catalyst is impacted by both the concentration and choice of monomers and inhibitors, usually organophosphorus derivatives. Herein we report a data-science-driven workflow to evaluate how these factors impact both the rate of FROMP and how long the formulation of the mixture is stable (pot life). Using this workflow, we built a classification model using a single-node decision tree to determine how a simple phosphine structural descriptor () can bin long versus short pot life.

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We developed a convergent strategy to build, cyclize and excise nitrogen from tertiary amines for the synthesis of polyheterocyclic aromatics. Biaryl-linked azepine intermediates can undergo a deaminative ring contraction cascade reaction, excising nitrogen with the formation of an aromatic core. This strategy and deaminative ring contraction reaction are useful for the synthesis of benzo[]quinolines.

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Synthetic organic electrosynthesis has grown in the past few decades by achieving many valuable transformations for synthetic chemists. Although electrocatalysis has been popular for improving selectivity and efficiency in a wide variety of energy-related applications, in the last two decades, there has been much interest in electrocatalysis to develop conceptually novel transformations, selective functionalization, and sustainable reactions. This review discusses recent advances in the combination of electrochemistry and homogeneous transition-metal catalysis for organic synthesis.

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Article Synopsis
  • Current methods for breaking carbon-nitrogen (C-N) bonds involve preparing specific derivatives from alkyl amines to facilitate the cleavage process.
  • A new technique combines in situ methylation of amines and nickel (Ni)-catalyzed C-N bond cleavage under specific conditions, enabling the transfer of alkyl groups from tertiary amines.
  • This innovative approach allows for multiple benzalkyl group transfers and constructs carbon-carbon (Csp-Csp) bonds efficiently using the methylation reagent PO(OMe).
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