Total Synthesis of Gelsemiol

Abstract

Let it grow! The neuritogenic iridoid gelsemiol has been prepared in synthetic form by a radical cascade and skeletal rearrangement. This compound accelerates the differentiation of neurons and growth of neuritis (see scheme).

Neuritogenic Surfaces using Natural Product Analogs

“…These slides were placed in a new 24-well plate, dried, and sterilized under UV-light irradiation for 2 h. NGF-primed PC12 cells were then grown on these slides and incubated for 2 d, fi xed, stained, and examined following known procedures. [ 24,[40][41][42][43] Signifi cantly enhanced neuronal differentiation on the slides coated with compound 1 has been observed, which supported our initial hypothesis ( Figure S1, Supporting Information). The ease and operational simplicity of this coating approach using a solution of the neuritogenic compound and a collagen matrix were found to be appealing.…”

Inverse‐Electron‐Demand Diels–Alder Reactions of 2‐Pyrones: Bridged Lactones and Beyond

“…The enantioselective IEDDA reaction of 3-carbomethoxy-2pyrone with vinylselenide wasa ppliedb yG ademanna nd coworkers to complete the total synthesis of (+ +)-gelsemiol, an oxidizedi ridoid first isolated from Gelsemium sempervirens. [82] As shown in Scheme 73, bicyclic lactone 363 was obtained in 91 %y ield and with 83 % ee value by aC u(OTf) 2 /BOX ligand-catalyzed enantioselective IEDDA reaction under reduced pressure, followed by radical-mediated and acid-catalyzed skeletal rearrangements to deliver bicyclic fused lactones 364 a and 364 b as ad iastereomericm ixture. Subsequently,l actones 364 underwent af our-step procedure involving methylation, lactone opening, ester hydrolysis and iodolactonization in one pot to furnishh ighly functionalized bicyclic fused lactone 365.…”

Asymmetric Inverse-Electron-Demand Diels–Alder Reactions of 2-Pyrones by Lewis Acid Catalysis

“…Notably, Gademann and co-workers elegantly extended this IED-DA reaction/rearrangement strategy to a substituted vinyl selenide 10 (up to 84% ee). 11 On the basis of this method, they completed a concise total synthesis of (+)-gelsimiol (12; Scheme 6).…”