Rearrangement of 2-azanorbornenes to tetrahydrocyclopenta[c]pyridines under the action of activated alkynes – A short pathway for construction of the altemicidin core

• Published in: Tetrahedron letters 2017-11, Vol.58 (46), p.4384-4387
• Main Authors: Nasirova, Dinara K., Malkova, Anastasia V., Polyanskii, Kirill B., Yankina, Kristina Yu, Amoyaw, Prince N.-A., Kolesnik, Irina A., Kletskov, Alexey V., Godovikov, Ivan A., Nikitina, Eugeniya V., Zubkov, Fedor I.
• Format: Article
• Language: English
• Subjects: 2-Azabicyclo[2.2.1]hept-5-ene; 2-Azanorbornene; Altemicidin; Amino-Claisen rearrangement; Cyclopenta[c]pyridine; DMAD
• ISSN: 0040-4039; 1873-3581
• DOI: 10.1016/j.tetlet.2017.10.015

[Display omitted] •Amino-Claisen rearrangement of azabicyclo[2.2.1]heptenes under the action of alkynes.•Diastereoselective pathway to altemicidin and dinklageine core analogs.•Effective synthesis of 2,4a,7,7a-tetrahydrocyclopenta[c]pyridines under mild conditions.•Short pathway for construction of the altemicidin core. A simple approach to a series of 2,4a,7,7a-tetrahydro-1H-cyclopenta[c]pyridines was proposed on the basis of the amino-Claisen rearrangement of readily accessible 2-azabicyclo[2.2.1]hept-5-enes under the action of dialkyl acetylenedicarboxylates, methyl propiolate or propiolamide. The rearrangement is highly diastereoselective and leads to the formation of only one isomer with cis-annulation of the five- and six-membered rings in satisfactory yields. Using the developed method, close analogs of the altemicidin and SB-203207 cores were synthesized.