Total syntheses of melinonine-E and strychnoxanthine: Evolution of the synthetic strategy enabled by novel method development

Abstract In this full account, the evolution of a synthetic strategy was detailed from a nitroso-ene cyclization to an aza-Wacker reaction for ring construction in the syntheses of melinonine-E and strychnoxanthine. The aza-Wacker cyclization to form the bridged ring was successfully developed and applied in the first asymmetric syntheses of melinonine-E and strychnoxanthine in 5–6 steps from a readily available chiral lactone. The proposed biogenesis of these two rare β-carbolinium alkaloids was revised based on their absolute configurations. Moreover, the substrate scope of the aza-Wacker cyclization demonstrated its potential for accessing various bridged ring skeletons. The mechanistic investigation established that the profound effect of the N-substituent on the amide was crucial to the success of the cyclization via the tunable amidopalladation pathway.

• Publication year

  2018

• Venue

  Tetrahedron

• Publication date

  2018-10-01

• Fields of study

  Chemistry

• Identifiers
  DOI 10.1016/J.TET.2018.08.015
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar

• No claims are published for this paper.

• No concepts are published for this paper.

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