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Base‐Mediated Generation of Ketenimines from Ynamides: [3+2] Annulation with Azaallyl Anions
Author(s) -
D'Hollander Agathe C. A.,
Romero Eugénie,
Vijayakumar Kamsana,
Le Houérou Camille,
Retailleau Pascal,
Dodd Robert H.,
Iorga Bogdan I.,
Cariou Kevin
Publication year - 2021
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202100047
Subject(s) - chemistry , cycloaddition , annulation , stereoselectivity , adduct , base (topology) , nitrogen , reactive intermediate , computational chemistry , combinatorial chemistry , photochemistry , organic chemistry , catalysis , mathematical analysis , mathematics
Under basic conditions and heat, ynamides can serve as precursors to ketenimines, whose synthetic potential is often hampered by their difficulty of access. Herein, we report that they can undergo a [3+2] cycloaddition with 2‐azaallyl anions, obtained from benzylimines under the same reaction conditions. This reaction between two highly reactive intermediates, both generated in situ from bench stable starting materials, gives access to various nitrogen‐rich heterocycles. The reaction usually proceeds with excellent diastereoselectivity, in favor of the cis adduct. Deuteration experiments and DFT calculations helped rationalize the regio‐ and stereoselectivity of the process as well as the formation of side products.