Vinylogous allylic sources

The insight gained from exposure of 36 to oxidants led us to the successful work from the Flowers group utilizing a cerium-mediated oxidative allylation of vinylogous amides [42]. Their investigations used a more soluble source of Ce(IV)... 

Allylic Sources Ambident Nucleophiles Better Donors Increase Reactivity Vinylogous Allylic Sources Allyiic Alkyne Sources... 

Vinylogous allylic sources, Z-C=C-C=C or Z-C=C-C=0, commonly react at the center atom and therefore will be treated as a subset of this source. A few examples of these vinylogous allylic electron sources are, respectively, extended enolates, acetoacetates, and malonates. 

These deprotonations generate extended enoiates, which are vinylogous allylic sources. Deprotonation can also occur on the methyl next to the carbonyl in the following example. However, the extended enolate is more delocalized. Section 9.3 covers the regiochemistry and stereochemistry of enolate formation in more detail. 

An allylic electron source can be considered to be a vinylogous lone pair. Sometimes the lone pair itself is the nucleophile and can undergo reactions similar to the... 

An allylic electron source can be considered to be a vinylogous lone pair. Sometimes the lone pair itself is the nucleophile and can undergo reactions similar to the lone pair sources in the first column of the matrix. However, most often the nucleophile is the end carbon atom of the pi bond. The heteroatom lone pair is much harder than the pi bond, and the decision of which to use as the nucleophile is based on the hardness of the electrophile (HSAB principle) and will be discussed at greater length in Section 9.4. 

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