Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 28, Issue 60, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202201637
Keywords
C-N bond formation; cyclization; Marcus inverted region; radical anion; two-center three-electron bond
Categories
Funding
- National Science Foundation [CHE-2102579]
- Projekt DEAL
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In this study, the possibility of oxidation under basic conditions for cross-dehydrogenative coupling (CDC) to form three-electron bonds was explored, which allows the use of milder oxidants and avoids the formation of high-energy intermediates.
Traditionally, cross-dehydrogenative coupling (CDC) leads to C-N bond formation under basic and oxidative conditions and is proposed to proceed via a two-electron bond formation mediated by carbenium ions. However, the formation of such high-energy intermediates is only possible in the presence of strong oxidants, which may lead to undesired side reactions and poor functional group tolerance. In this work we explore if oxidation under basic conditions allows the formation of three-electron bonds (resulting in upconverted highly-reducing radical-anions). The benefit of this upconversion process is in the ability to use milder oxidants (e. g., O-2) and to avoid high-energy intermediates. Comparison of the two- and three-electron pathways using quantum mechanical calculations reveals that not only does the absence of a strong oxidant shut down two-electron pathways in favor of a three-electron path but, paradoxically, weaker oxidants react faster with the upconverted reductants by avoiding the inverted Marcus region for electron transfer.
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