Search

Your search keyword '"Drappeau, Justine A."' showing total 5 results
Start Over Author "Drappeau, Justine A."
5 results on '"Drappeau, Justine A."'

2. C(sp3)−H (N‐Phenyltetrazole)thiolation as an Enabling Tool for Molecular Diversification.

Author

Zachmann, Ashley K. Z., Drappeau, Justine A., Liu, Shubin, and Alexanian, Erik J.

Subjects
*RADICALS (Chemistry), *CHEMICAL synthesis, *COUPLING reactions (Chemistry), *FUNCTIONAL groups, *HYDROGEN bonding, *ABSTRACTION reactions
Abstract

Methods enabling the broad diversification of C(sp3)−H bonds from a common intermediate are especially valuable in chemical synthesis. Herein, we report a site‐selective (N‐phenyltetrazole)thiolation of aliphatic and (hetero)benzylic C(sp3)−H bonds using a commercially available disulfide to access N‐phenyltetrazole thioethers. The thioether products are readily elaborated in diverse fragment couplings for C−C, C−O, or C−N construction. The C−H functionalization proceeds via a radical‐chain pathway involving hydrogen atom transfer by the electron‐poor N‐phenyltetrazolethiyl radical. Hexafluoroisopropanol was found to be essential to reactions involving aliphatic C(sp3)−H thiolation, with computational analysis consistent with dual hydrogen bonding of the N‐phenyltetrazolethiyl radical imparting increased radical electrophilicity to facilitate the hydrogen atom transfer. Substrate is limiting reagent in all cases, and the reaction displays an exceptional functional group tolerance well suited to applications in late‐stage diversification. [ABSTRACT FROM AUTHOR]

Published
2024
Full Text
View/download PDF

3. Consequences of ligand derivatization on the electronic properties of polyoxovanadate-alkoxide clusters

Author

Schurr, Bradley E., Nachtigall, Olaf, Vangelder, Lauren E., Drappeau, Justine, Brennessel, William W., and Matson, Ellen M.

Abstract

Polyoxovanadate-alkoxide (POV-alkoxide) clusters are promising charge-carrier candidates for non-aqueous redox flow batteries (NRFBs), due in part to their easily-modified bridging alkoxide ligands. Herein, we report a series of new POV-alkoxide clusters featuring polar functional groups bound to the tertiary carbon of a tripodal, tris(hydroxymethyl)methane ligand (TRISR; R = C2H5, NO2, NMe3+, NC5H4 (Py), PyMe+). These clusters were synthesized to better understand the role that peripheral ligands with varying electronic properties play in tuning the electrochemical profile of the hexavanadate core. The results herein demonstrate that functional groups removed from the cluster core do not disrupt the characteristic electrochemical behavior of the mixed-valent POV-alkoxides, establishing the synthetic modularity of this structural platform. However, in contrast to molecular species previously reported, these polar and charged functional groups do not improve solubility or stability of the charge carriers in acetonitrile. This work furthers our knowledge of coordination chemistry of POV-ethoxide clusters, presenting design criteria critical for accessing polynuclear entities ideal for NRFB charge carriers.

Published
2019
Full Text
View/download PDF

5. C(sp 3 )-H (N-Phenyltetrazole)thiolation as an Enabling Tool for Molecular Diversification.

Author

Zachmann AKZ, Drappeau JA, Liu S, and Alexanian EJ

Abstract

Methods enabling the broad diversification of C(sp 3 )-H bonds from a common intermediate are especially valuable in chemical synthesis. Herein, we report a site-selective (N-phenyltetrazole)thiolation of aliphatic and (hetero)benzylic C(sp 3 )-H bonds using a commercially available disulfide to access N-phenyltetrazole thioethers. The thioether products are readily elaborated in diverse fragment couplings for C-C, C-O, or C-N construction. The C-H functionalization proceeds via a radical-chain pathway involving hydrogen atom transfer by the electron-poor N-phenyltetrazolethiyl radical. Hexafluoroisopropanol was found to be essential to reactions involving aliphatic C(sp 3 )-H thiolation, with computational analysis consistent with dual hydrogen bonding of the N-phenyltetrazolethiyl radical imparting increased radical electrophilicity to facilitate the hydrogen atom transfer. Substrate is limiting reagent in all cases, and the reaction displays an exceptional functional group tolerance well suited to applications in late-stage diversification., (© 2024 Wiley-VCH GmbH.)

Published
2024
Full Text
View/download PDF

Catalog

Books, media, physical & digital resources
See catalog results