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Abstract [3+n]‐Cycloaddition reactions that employ donor‐acceptor cyclopropanes using either chiral catalysts and racemic cyclopropanes or achiral catalysts and chiral, non‐racemic, cyclopropanes have become useful transformations for the construction of carbocyclic and heterocyclic compounds, with both processes offering mechanistic and structural advantages in ring formation. Although the vast majority of asymmetric cycloaddition reactions of donor‐acceptor cyclopropanes have been performed with racemic cyclopropane compounds catalyzed by Lewis acids with chiral ligands, optically active cyclopropane compounds can serve the same role using Lewis acids without chiral ligands. This review covers the use of chiral catalysts with racemic donor‐acceptor cyclopropanes and the use of chiral non‐racemic donor‐acceptor cyclopropanes with achiral Lewis acid catalysts.
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Converting Strain Release into Aromaticity Loss for Activation of Donor–Acceptor Cyclopropanes: Generation of Quinone Methide Traps for C-Nucleophiles
Here, we present a new approach for the activation of donor–acceptor cyclopropanes in ring-opening reactions, which does not require the use of a Lewis or Brønsted acid as a catalyst. Donor–acceptor cyclopropanes containing a phenolic group as the donor undergo deprotonation and isomerization to form the corresponding quinone methides. This innovative strategy was applied to achieve (4 + 1)-annulation of cyclopropanes with sulfur ylides, affording functionalized dihydrobenzofurans. Additionally, the generated ortho- and para-(aza)quinone methides can be trapped by various CH-acids.
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- Award ID(s):
- 2102579
- PAR ID:
- 10587676
- Publisher / Repository:
- ACS
- Date Published:
- Journal Name:
- Organic Letters
- Volume:
- 26
- Issue:
- 38
- ISSN:
- 1523-7060
- Page Range / eLocation ID:
- 8177 to 8182
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.orglett.4c03106
