AI Article Synopsis
- Altering the reactivity of molecules could resolve current limitations, especially for Donor-Acceptor Cyclopropanes (DACs) which have relied on Lewis acids for activation.
- Unpolarized alkenes present challenges due to a polarity mismatch with the Lewis acid-mediated zwitterionic intermediate, hindering their coupling.
- Using photoredox catalysis to leverage the distonic radical cation approach successfully navigates this mismatch, allowing for the formation of highly substituted cyclopentanes and facilitating new pathways to create bicyclo[3.1.1]heptanes through a unique [3σ+2σ] cycloaddition process.
Article Abstract
Altering the reactivity model of a molecule can potentially eliminate limitations existing in its current paradigm. When it comes to the activation of Donor-Acceptor Cyclopropanes (DACs), Lewis acids have been the state-of-the-art. Although a variety of polarized 2π components have been successfully coupled with DACs for [3+2] cycloaddition, unpolarized alkenes prove to be a roadblock due to an inherent polarity mismatch with the Lewis acid-mediated 1,3-zwitterionic intermediate. Hereby, harnessing the distonic radical cation mode of cleavage by photoredox catalysis overcomes this mismatched reactivity of the zwitterionic intermediate, providing a unique route to highly substituted cyclopentanes and cyclopentenes. Expansion of this strategy to bicyclo[1.1.0]butanes enables access to bicyclo[3.1.1]heptanes (BCHs) through a facile [3σ+2σ] cycloaddition. Detailed mechanistic insights are also provided using dispersion-corrected density functional theory.
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| http://dx.doi.org/10.1002/anie.202419426 | DOI Listing |
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