Acyclic 1,4-Stereocontrol via the Allylic Diazene Rearrangement: Development, Applications, and the Essential Role of Kinetic E Stereoselectivity in Tosylhydrazone Formation.
In: Journal of Organic Chemistry, Jg. 82 (2017-08-18), Heft 16, S. 8359-8370
academicJournal
Zugriff:
We report full details of a method for 1,3-reductive transposition of α-alkoxy-α,β-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 allylic strain controlled retro-ene reaction of an allyl diazene, i.e., 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. [ABSTRACT FROM AUTHOR]
Titel: |
Acyclic 1,4-Stereocontrol via the Allylic Diazene Rearrangement: Development, Applications, and the Essential Role of Kinetic E Stereoselectivity in Tosylhydrazone Formation.
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Autor/in / Beteiligte Person: | Shrestha, Maha L. ; Qi, Wei ; McIntosh, Matthias C. |
Zeitschrift: | Journal of Organic Chemistry, Jg. 82 (2017-08-18), Heft 16, S. 8359-8370 |
Veröffentlichung: | 2017 |
Medientyp: | academicJournal |
ISSN: | 0022-3263 (print) |
DOI: | 10.1021/acs.joc.7b00428 |
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