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An alkenyl group is a monovalent carbon–hydrogen substituent derived from an alkene by removing one hydrogen atom. The attachment can be at a double-bonded carbon or elsewhere in the carbon skeleton. For an acyclic parent with one double bond, the group composition is ${\mathrm{C}}_{\mathrm{n}}{\mathrm{H}}_{2n-1}$.^[ref]

For example, a vinyl group attaches as $\mathrm{R}-\mathrm{CH}=\mathrm{C}{\mathrm{H}}_2$ and contributes ${\mathrm{C}}_2{\mathrm{H}}_3$, whereas an allyl group attaches as $\mathrm{R}-\mathrm{C}{\mathrm{H}}_2-\mathrm{CH}=\mathrm{C}{\mathrm{H}}_2$ and contributes ${\mathrm{C}}_3{\mathrm{H}}_5$. The attachment atom in the first example belongs to the double bond; in the second it is adjacent to the double bond. A prenyl group is another alkenyl group, with five carbon atoms.^[ref]

The missing hydrogen identifies an attachment site in a larger molecule; it does not mean that the completed attached group must contain an unpaired electron. Formulae alone also do not specify connectivity. For $n=3$, the composition ${\mathrm{C}}_3{\mathrm{H}}_5$ does not by itself tell where the attachment or double bond lies. A structural formula supplies information that the atom count omits.

The compound $\mathrm{C}{\mathrm{H}}_2=\mathrm{CHC}{\mathrm{H}}_2\mathrm{Br}$. nucleophilic substitution at its bromomethylene carbon introduces an allyl group without consuming the alkene.

The first base equivalent removes O–H; the second removes the alpha C–H. The first equivalent of lithium diisopropylamide converts the carboxylic acid to its lithium carboxylate. A further equivalent removes the remaining hydrogen on the carbon between the two allyl groups, giving a carboxylic acid dianion:The second negative charge has enolate-like delocalization into the carboxyl group; lithium coordination and aggregation are not represented by this simple charge-bookkeeping structure. The carbon nucleophile attacks methyl iodide with C–I bond cleavage, forming the new C–Me bond. acid workup reprotonates the carboxylate, giving $F=\mathrm{H}{\mathrm{O}}_2\mathrm{C}-\mathrm{C}(\mathrm{Me})(\mathrm{L}{)}_2$. The two equivalents are therefore chemically necessary for the stated carbon alkylation rather than simply an arbitrary excess. A single equivalent is consumed predominantly by the much more acidic carboxylic proton. The product has formula ${\mathrm{C}}_9{\mathrm{H}}_{14}{\mathrm{O}}_2$ and still has two identical allyl groups, so this methylation does not create a stereocenter.

The malonate carbon receives two allyl groups. With $L=\mathrm{C}{\mathrm{H}}_2\mathrm{CH}=\mathrm{C}{\mathrm{H}}_2$, attached through its first carbon, the product issodium hydride removes a methylene proton from diethyl malonate; molecular hydrogen formation accompanies production of an enolate stabilized by resonance in chemistry. Its carbon attacks the bromomethylene carbon of allyl bromide in an SN2 reaction, expelling bromide. The monoalkylated malonate still has one hydrogen between the carbonyls. Excess base removes that hydrogen, and a second equivalent of allyl bromide produces a second carbon–carbon bond. The final malonate carbon has no remaining hydrogen and cannot undergo a third analogous deprotonation there.

The two alkenes are preserved because the substitution occurs at the primary carbon bearing bromine. Counting the introduced groups gives ${\mathrm{C}}_{13}{\mathrm{H}}_{20}{\mathrm{O}}_4$ for the diallylated diethyl ester. Its two identical allyl groups also mean that the central carbon is not a stereocenter. This stage is the alkylation portion of the malonic ester synthesis.

The first reagent supplies a vinyl nucleophile, $\mathrm{C}{\mathrm{H}}_2=\mathrm{CH}-$, rather than an allyl group. Two successive conjugate additions install vinyl at C2 and a 2-formylethyl chain at C1. Number the original nitro-bearing alkene carbon C1. Vinylmagnesium bromide attacks the beta carbon C2 of the nitroalkene, shifting the original C1=C2 electrons into a magnesium nitronate. The new C2–vinyl bond remains intact during the second stage; its terminal double bond is not the electrophilic site in that stage.

The carbon end of the nitronate at C1 then attacks the terminal beta carbon of acrolein. Move the acrolein C=C electrons towards its carbonyl and the C=O electrons onto oxygen. This forms the C1–CH2CH2CHO connectivity through an aldehyde enolate; protonation by methanol and tautomerization restore the aldehyde. The nitronate returns to a neutral nitro group as it makes the second C–C bond. Thus the chain is attached through the carbon formerly beta to the acrolein carbonyl, rather than by a direct addition to its aldehyde carbon.

After the first addition, C2 bears the vinyl group while the nitronate carbon C1 remains approximately planar. Approach of the second electrophile to the less crowded face, opposite the adjacent vinyl substituent, gives the new formylethyl chain trans to vinyl. Consequently nitro and vinyl are cis, as depicted: at C1 the chain and nitro group occupy opposite faces. This is a substrate-controlled diastereoselective tandem Michael addition. The reagents and starting material contain no chiral source, so the depicted product represents a racemic pair rather than an enantioselective synthesis. Steric facial selection explains the relative configuration without requiring a uniquely established magnesium aggregate or transition-state conformation.

The specific five-carbon prenyl group is the alkenyl group 3-methylbut-2-en-1-yl, with connectivityHere $\mathrm{R}$ is the rest of the attached molecule; the prenyl group itself has composition ${\mathrm{C}}_5{\mathrm{H}}_9$. The ChEBI structural record uses SMILES *CC=C(C)C, with the asterisk marking the attachment point.^[ref]

The count is instructive: the attachment-end $\mathrm{C}{\mathrm{H}}_2$ contributes one carbon and two hydrogen atoms; $\mathrm{CH}$ contributes one and one; the next double-bonded carbon contributes no hydrogen; and the two methyl groups contribute two carbon and six hydrogen atoms. Together these give five carbon and nine hydrogen atoms. The double bond is one bond away from the attachment atom, connecting the prenyl group with the broader allyl group pattern.

Attaching the group through oxygen gives $\mathrm{R}-\mathrm{O}-\mathrm{C}{\mathrm{H}}_2-\mathrm{CH}=\mathrm{C}(\mathrm{C}{\mathrm{H}}_3{)}_2$, a prenyl ether; attachment through another atom gives a different linkage. The same carbon fragment therefore does not specify the whole functional group environment. In biological prenylation, the terminology can also encompass longer isoprenoid-derived attachments, so the particular transferred group must be stated.

The group $\mathrm{C}{\mathrm{H}}_2=\mathrm{CH}-$, attached through an alkene carbon. It differs from an allyl group, whose attachment includes an intervening methylene.