η2-Coordination of Phenyl Sulfones: A Modular Synthetic Platform for Accessing Functionalized Cyclohexenes and Heteropolycyclic Cores 32 views

As medicinal chemistry has evolved, increasing emphasis has been placed on methodologies capable of rapidly generating molecular complexity and diversity. In particular, synthetic strategies that provide access to key structural elements, such as 3-dimensionality (sp3 centers) and fused polycyclic frameworks, have become increasingly important. To this end, the Harman lab has sought to provide stereo- and regio-selective access to a wide range of substituted cyclohexenes via transition metal-mediated dearomatization. The current generation of this work centers on η2-coordination of benzene derivatives to [WTp(NO)(PMe3)] (Tp= trispyrazolylborate), activating the bound arene through a metal dπ to π* backbonding interaction. This activation, along with the steric bulk of the tungsten fragment, predictably and stereoselectively directs subsequent electrophilic and nucleophilic additions to the unbound portions of the ring. My research has focused on the η2-coordination of phenyl sulfones as a platform for the modular synthesis of three-dimensionally enriched and natural product-inspired scaffolds. Through the development of new functionalization and annulation strategies about the bound arene, all four unbound stereocenters can be selectively elaborated to access diverse cis-fused heteropolycyclic cores. Subsequent liberation from the metal center affords the corresponding organic products, demonstrating the utility of η2-phenyl sulfone complexes as a versatile route towards complex and biologically relevant molecular architectures.

PHD (Doctor of Philosophy)

dearomatization; natural product-like; dihapto-coordination; polycyclic; transition metal mediated; synthetic methodology

English

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2026-07-30