For the first time in more than one-hundred years, we have liberated radical-mediated C–H functionalization reactions from the constraints of a canonical mechanistic step that has limited and dictated the site of a broad class of C–H functionalization reactions (Hofmann-Löffler-Freytag reactions). Our laboratory has pioneered an approach designed to harness substrate geometry to develop otherwise rare C–H functionalization processes. Our approach is innovative as prior methods to dictate the site of reaction have relied on the inherent properties of the carbon framework of a molecule, or of a metal, to dictate the site of a reaction, rather than on the geometry of a transiently installed tether, known as a dialkyl sulfamate ester or sulfamide (i.e. sulfamic acid analogue). The premise of this research is that alcohol- and amine-anchored functional groups can support nitrogen-centered radicals, and be designed such that the geometry of these groups would dictate the site of C–H functionalization reactions. This talk will engage this novel strategy to harness alcohols and amines to replace C–H bonds at gamma-C(sp3)–H centers, which are not generally accessible to directed functionalization reactions. We will demonstrate that C–H abstraction can be robustly coupled with varied functionalization reactions. This talk will highlight the first generalizable synthetic strategy to functionalize gamma-C(sp3)–H bonds based on masked alcohols or amines, to push the boundaries of organic chemistry at a fundamental level and benefits drug discovery.

Using substrate geometry to dictate the site of C–H functionalization reactions

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.