Rui Fan, Yuewei Wen and Dasan M. Thamattoor
Org. Biomol. Chem., 2017,15, 8270-8275
DOI:
10.1039/C7OB01697B,
Communication
The strained heterocyclic alkyne, 3-oxacyclohexyne, was generated photochemically for the first time using a cyclopropanated phenanthrene precursor, and trapped by cyclopentadienones as Diels–Alder adducts. The precursor initially produced the putative 3-oxacyclopentylidenecarbene that subsequently rearranged to the cycloalkyne. Computational studies indicate that the carbene favors a singlet state, and the barrier for its ring expansion by a 1,2-shift of the carbon proximal to oxygen is lower in energy than the corresponding shift of the distal carbon.