Structural effects on sigmatropic shifts in heteroaromatic allyl ethersElectronic supplementary information (ESI) available: selected crystal data for compound 7. See

Nuna C. P. Araújo, Pedro M. M. Barroca, Jamie F. Bickley, Amadeu F. Brigas, M. Lurdes S. Cristiano, Robert A. W. Johnstone, Rui M. S. Loureiro, Paula C. A. Pena
2002 Perkin 1  
In contrast to the known thermal, exclusively [3,3], O-to N-rearrangement of allyl groups in phenyltetrazoles (1, Scheme 1), the comparable migration of the allyl group in pseudosaccharyl ethers (3; Scheme 2) has been shown to proceed through both [1,3]-and [3,3]-mechanisms, 4, 5; for the pseudosaccharyl derivative of the natural product myrtenol (6; Scheme 3) only the product 7 of a [1,3]-shift has been observed; crystallographic data and theoretical calculations provide an explanation of this
more » ... ease of [1,3]-isomerization and the observed selectivity as being due to conformational constraints and electronic factors.
doi:10.1039/b102674g fatcat:x6q4hzb3ingilks27ppf3rhppi