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Award ID contains: 1856747

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  1. Abstract A strategy to control the diastereoselectivity of bond formation at a prochiral attached‐ring bridgehead is reported. An unusual stereodivergent Michael reaction relies on basic vs. Lewis acidic conditions and non‐covalent interactions to controlre‐ vs.si‐ facial selectivity en route to fully substituted attached‐rings. This divergency reflects differential engagement of one rotational isomer of the attached‐ring system. The successful synthesis of anerythrosubtarget diastereomer ultimately leads to a short formal synthesis of merrilactone A. 
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  2. Stitching and then reducing aromatic building blocks offers an efficient route into alkaloids found in Galbulimima bark. 
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  3. Covering: 2000 to 2020 The hallucinogenic diterpene salvinorin A potently and selectively agonizes the human kappa-opioid receptor (KOR). Its unique attributes-lack of a basic nitrogen, rapid brain penetrance, short half-life-combined with the potential of KOR as an emerging target for analgesics have stimulated extensive medicinal chemistry based on semi-synthesis from extracts of Salvia divinorum . Total synthesis efforts have delivered multiple, orthogonal routes to salvinorin A, its congeners and related analogs with the goal of optimizing its activity towards multiple functional endpoints. Here we review total syntheses of the salvinorin chemotype and discuss outstanding problems that synthesis can address in the future. 
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