Acyclic 1,4-Stereocontrol via the Allylic Diazene Rearrangement: Development, Applications, and the Essential Role of Kinetic E Stereoselectivity in Tosylhydrazone Formation
by Shrestha, Maha L.; Qi, Wei; McIntosh, Matthias C.
We report full details of a method for 1,3 reductive transposition of alpha-alkoxy-alpha,beta-unsaturated hydrazones to provide E-alkenes with high 1,4-stereocontrol between the two respective allylic stereocenters. The process couples a chelation-controlled reduction of the hydrazone with an in situ strain controlled retro-ene reaction Of an, allyl diazene, an allylic ,diazene rearrangement. Such stereotriads are frequently observed. motifs in natural products. We observed a fortuitous kinetic preference for the E-hydrazone geometry during the hydrazonation reaction, as only the E-isomers could undergo chelation-controlled reduction.
- Journal
- Journal of Organic Chemistry
- Volume
- 82
- Issue
- 16
- Year
- 2017
- Start Page
- 8359-8370
- URL
- https://dx.doi.org/10.1021/acs.joc.7b00428
- ISBN/ISSN
- 1520-6904; 0022-3263
- DOI
- 10.1021/acs.joc.7b00428