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DOI: 10.1055/s-0040-1706282
Simple Synthesis of Complex Amines from the Diels–Alder Adducts of (–)-Cytisine
This work was supported by Life Chemicals Inc.


Abstract
The Diels–Alder reaction of N-benzylcytisine with N-methyl- and N-benzylmaleimides is 100% endo-selective and gives the corresponding syn- and anti-diastereomers in 11–42% isolated yields. The studies of the reaction progress with LCMS and NMR along with detailed quantum chemical calculations revealed that some Diels–Alder adducts are kinetically and their isomers are thermodynamically controlled products. The Pd/C-catalyzed hydrogenation of benzyl-protected cytisine amine derivatives resulted in the removal of the benzyl group and the addition of hydrogen to the C=C double bond to give the corresponding secondary amines in 45–84% yield. The complete reduction of carbonyl groups in a cytisine derivative with LiAlH4 in THF under reflux afforded the respective tricyclic triamine. Quantum mechanical calculations for the mechanism of the Diels–Alder reaction between the simplest model compounds are presented.
Key words
cytisine - maleimides - Diels–Alder reaction - diastereoselectivity - hydrogenation - LiAlH4 reduction - quantum chemical calculationsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1706282.
- Supporting Information
Publikationsverlauf
Eingereicht: 13. April 2021
Angenommen nach Revision: 02. Juli 2021
Artikel online veröffentlicht:
16. August 2021
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