An investigation of the [3,3]-sigmatropic reaction of
substituted 3-aza-1,2,5-hexatrienes to give
4-pentenenitriles is presented. This reaction has been found to
occur under a wide variety of
reactions conditions (10 are reported) starting from readily available
N-allylamides. In contrast
to other 3-aza-Cope reactions, this process occurs at room temperature,
under essentially neutral
conditions, allowing for the facile preparation of substituted nitrile
products in moderate to excellent
yields. The scope and versatility of this reaction are
demonstrated by its use on a wide variety of
substrates, including nitrogen- and oxygen-substituted amides. The
rearrangements of cis- and
trans-4-tert-butyl-N-allylcyclohexanecarboxamides
16a and 16b are reported and were found
to
give a ratio of axial to equatorial (A:E) products consistent with A:E
ratios found for other related
sigmatropic reactions. The stereochemical requirements for this
reaction appear to be similar to
other [3,3]-rearrangements even though the transition state for this
rearrangement is most likely
neither boat nor chairlike.
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ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
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