SRIBS – Srinivasa Ramanujan Institute for Basic Sciences

Sugunan, A., Ahirwar, M. B., Suresh, C. H., Deshmukh, M. M., & Rajendar, G. (2024). Cooperative noncovalent interactions controlling amine-catalyzed aldol reaction pathways catalyzed by bifunctional amino quaternary phosphonium ion. Journal of Organic Chemistry, 89(16), Article 4c01635.

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https://doi.org/10.1021/acs.joc.4c01635

Abstract: Members of a new class of bifunctional amino quaternary phosphonium salts have been synthesized and utilized as catalysts in aldol condensation reactions, as demonstrated herein. These secondary amines feature a phosphonium ion connected by a carbon chain, enabling the quaternary phosphonium ion to engage in distinct cooperative noncovalent interactions. These interactions work in tandem to stabilize different transition state complexes, exclusively controlling competing amine-catalyzed aldol pathways via the Mannich mechanism. Comprehensive mechanistic investigations were conducted through theoretical calculations. This study uncovers a proximity-driven catalytic mechanism in which the distance between the N and the P+ of the bifunctional catalyst emerges as a critical factor determining catalytic efficacy. The method has been demonstrated through its application to the total synthesis of several bioactive natural products.

ionic-interaction

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