Described herein is a function‐oriented synthesis route and biological evaluation of pseudoguaianolide analogues. The 10‐step synthetic route developed retains the topological complexity of the natural product, installs functional handles for late‐stage diversification, and forges the key bioactive Michael acceptors early in the synthesis. The analogues were found to be low‐micromolar Nrf2 activators and micromolar NF‐κB inhibitors and dependent on the local environment of the Michael acceptor moieties.
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Abstract -
Herein reported is a strategy for constructing vicinal 4°/3° carbons via reductive Cope rearrangement. Substrates have been designed which exhibit Cope rearrangement kinetic barriers of ∼23 kcal mol −1 with isoenergetic favorability (Δ G ∼ 0). These fluxional/shape-shifting molecules can be driven forward by chemoselective reduction to useful polyfunctionalized building blocks.more » « less
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null (Ed.)Explored was the competitive ring-closing metathesis vs. ring-rearrangement metathesis of bicyclo[3.2.1]octenes prepared by a simple and convergent synthesis from bicyclic alkylidenemalono-nitriles and allylic electrophiles. It was uncovered that ring-closing metathesis occurs exclusively on the tetraene-variant, yielding unique, stereochemically and functionally rich polycyclic bridged frameworks, whereas the reduced version (a triene) undergoes ring-rearrangement metathesis to 5 – 6 – 5 fused ring systems resembling the isoryanodane core.more » « less
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null (Ed.)Functional group interconversions are essential chemical processes enabling synthesis. In this report, we describe a strategy to convert alkylidenemalononitriles into primary alcohols in one step. The reaction relies on a choreographed redox process involving alkylidene reduction, malononitrile oxidation, and acylcyanide reduction where molecular oxygen and NaBH4 work cooperatively. The method was applied to a variety of carbon skeletons and was utilized to synthesize complex terpenoid architectures.more » « less
