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Photochemical generation and trapping of 3-oxacyclohexyne
Rui Fan1, Yuewei Wen, Dasan M Thamattoor
1Department of Chemistry, Colby College, 5765 Mayflower Hill, Waterville, ME 04901, USA. dmthamat@colby.edu.
Abstract:
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.
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