A New Synthetic Tool: The Pseudo-Intramolecular Process.

Area of Science:

• Organic Chemistry
• Synthetic Methodology

Background:

• Developing efficient and versatile synthetic routes is crucial in organic chemistry.
• Traditional intermolecular reactions often lack the efficiency and selectivity of intramolecular counterparts.

Purpose of the Study:

• To introduce a new synthetic concept, the "pseudo-intramolecular process," for enhanced intermolecular reactions.
• To demonstrate the broad applicability of this concept in synthesizing valuable organic compounds.

Main Methods:

• Utilizing salt formation to induce spatial proximity between reacting substrates.
• Applying the pseudo-intramolecular concept to reactions involving alpha-aryl-beta-keto esters and alpha-nitro-beta-keto nitriles.

Main Results:

• Achieved high efficiency, regioselectivity, and chemoselectivity in transacylation reactions of alpha-aryl-beta-keto esters with amines.
• Synthesized polyfunctionalized azaheterocyclic compounds from alpha-nitro-beta-keto nitriles via tandem cyclization.
• Demonstrated that reactions proceed under mild conditions using simple experimental manipulations and without special reagents.

Conclusions:

• The pseudo-intramolecular process is a powerful and broadly applicable strategy in organic synthesis.
• This methodology offers a practical and efficient approach to constructing complex molecular architectures, including azaheterocycles.
• The developed protocols are valuable for their simplicity, mild conditions, and high selectivity.