key term - Intramolecular

Definition

Intramolecular refers to processes or interactions that occur within a single molecule, as opposed to intermolecular which involves interactions between different molecules. This term is particularly relevant in the contexts of Claisen condensations and peptide/protein structures.

5 Must Know Facts For Your Next Test

1. Intramolecular reactions occur within a single molecule, whereas intermolecular reactions involve interactions between separate molecules.
2. The Dieckmann cyclization is an important intramolecular Claisen condensation reaction that forms cyclic $\beta$-keto esters.
3. Peptide bonds, which link amino acids together in proteins, are an example of an intramolecular covalent interaction within a single polypeptide chain.
4. Intramolecular hydrogen bonding can stabilize certain molecular conformations, such as in the secondary structures of proteins.
5. Intramolecular nucleophilic attack is a key step in many cyclization reactions, including the Dieckmann cyclization.

Review Questions

• Explain the role of intramolecular interactions in the Dieckmann cyclization reaction.
  • In the Dieckmann cyclization, an intramolecular Claisen condensation occurs where the nucleophilic enolate of one ester group attacks the electrophilic carbonyl carbon of another ester group within the same molecule. This intramolecular process results in the formation of a cyclic $\beta$-keto ester product. The ability of the molecule to bring the reactive groups into close proximity is crucial for this intramolecular cyclization to take place.
• Describe how intramolecular interactions contribute to the secondary structure of proteins.
  • The secondary structure of proteins, such as $\alpha$-helices and $\beta$-sheets, is stabilized by intramolecular hydrogen bonding between the carbonyl oxygen and amino hydrogen atoms within the polypeptide backbone. These intramolecular hydrogen bonds help maintain the characteristic three-dimensional folding patterns of proteins, which are essential for their biological functions. The precise arrangement of these intramolecular interactions determines the overall secondary structure of the protein.
• Analyze the importance of intramolecular reactions in the context of organic chemistry.
  • Intramolecular reactions are crucial in organic chemistry because they allow for the formation of cyclic compounds and the creation of new functional groups and molecular scaffolds. The ability of a molecule to bring reactive groups into close proximity through intramolecular interactions enables a wide range of cyclization and rearrangement reactions, such as the Dieckmann cyclization. These intramolecular processes are often more efficient and selective than their intermolecular counterparts, making them valuable tools in organic synthesis and the construction of complex molecular structures.

Related terms

Claisen Condensation:

A type of carbon-carbon bond forming reaction that involves the condensation of two carbonyl compounds, typically esters or ketones, to form a $\beta$-keto ester.

Dieckmann Cyclization:

An intramolecular Claisen condensation reaction that results in the formation of a cyclic $\beta$-keto ester.

Peptide Bond:

A covalent chemical bond formed between the carboxyl group of one amino acid and the amino group of another, linking amino acids into a polypeptide chain.