Ring Transformation of Cyclopropenes to Benzo‐Fused Five‐Membered Oxa‐ and Aza‐Heterocycles via a Formal [4+1] Cyclization
heterocycles
late‐stage modifications
ring transformation
Science
cyclopropenes
rhodium
Q
DFT calculations
Research Article
0104 chemical sciences
DOI:
10.1002/advs.202407931
Publication Date:
2024-08-29T10:34:18Z
AUTHORS (11)
ABSTRACT
AbstractIn the context of the growing importance of heterocyclic compounds across various disciplines, numerous strategies for their construction have emerged. Exploiting the distinctive properties of cyclopropenes, this study introduces an innovative approach for the synthesis of benzo‐fused five‐membered oxa‐ and aza‐heterocycles through a formal [4+1] cyclization and subsequent acid‐catalyzed intramolecular O‐ to N‐ rearrangement. These transformations exhibit mild reaction conditions and a wide substrate scope. The applications in the late‐stage modification of complex molecules and in the synthesis of a potential PD‐L1 gene down‐regulator, make this method highly appealing in related fields. Combined experimental mechanistic studies and DFT calculations demonstrate Rh(III)‐mediated sequential C─H coupling/π‐allylation/dynamically favorable O‐attack route.
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