Carbon-based reactive species such as carbocations, carbanions, radicals, and carbenes are fundamental pillars in the logic of chemical synthesis. However, carbynes (the monovalent reactive carbon) have not being exploited as synthetic intermediates. Considering their unique ability to form three new covalent bonds, we reasoned that the discovery of a catalytic method to generate these species or their stabilizes forms would reveal previously elusive disconnection approaches and significantly advance the core of synthetic chemistry. Here, we report that photoredox catalysis, when applied to a designed diazo reagent, lead to unprecedented diazomethyl radicals as carbyne equivalents. The reactivity of the latter species with aryl C-H bonds underpins a useful assembly-point functionalization for chiral center synthesis, which has been exploited in the late-stage diversification of therapeutic agents.

Unlocking the elusive generation of carbyne equivalents with photoredox catalysis

254th National Meeting (2017)

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