Orbital-Overlap Control in the Solid-State Reactivity of β-Azido-Propiophenones: Selective Formation ofcis-Azo-Dimers
- 7 February 2008
- journal article
- research article
- Published by American Chemical Society (ACS) in Organic Letters
- Vol. 10 (5), 937-940
- https://doi.org/10.1021/ol703098q
Abstract
Solid-state photolysis of 1a,b yields selectively cis-3a,b. X-ray analysis of 1a,b reveals the molecules adopt an extended structure and as such the crystal packing arrangement consists of planar, π-stacked molecules. The shortest intermolecular distance between adjacent N-atoms is ∼3.76 Å and would lead to formation of trans-3a,b, whereas cis-3a,b is formed by dimerization between N-atoms that are ∼3.9 Å apart. We propose that the molecular orbital alignment of the adjacent nitrenes controls the solid-state reactivity.Keywords
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